Photosensitive resin composition, transfer film, method for manufacturing a resin pattern, and method for manufacturing a conductive pattern

Abstract

The present invention provides a photosensitive resin composition that can form resin patterns with improved shape defects and excellent resolution. [Solution] A photosensitive resin composition comprising an alkali-soluble resin containing a crosslinkable group having a double bond, a polyfunctional (meth)acrylate, and a polymerization inhibitor, wherein the total double bond content in the solids of the photosensitive resin composition is 2.00 mmol / g or more relative to the total amount of solids of the photosensitive resin composition, the proportion of double bonds based on acryloyl groups to the total number of double bonds in the solids of the photosensitive resin composition is 10% to 50%, and the molar ratio of the polymerization inhibitor content to the content of double bonds based on acryloyl groups is 0.001 to 0.015.

Description

[Technical Field]

[0001] This disclosure 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 manufacturing of printed circuit boards and the like, photosensitive resin compositions are widely used as resist materials.

[0003] For example, Patent Document 1 describes a bonding step of bonding a transfer film having a temporary support and a photosensitive composition layer to a substrate such that the surface of the transfer film opposite to the temporary support is in contact with the metal layer of a substrate having a metal layer on its surface; an exposure step of pattern exposure of the photosensitive composition layer; a developing step of performing a developing process on the exposed photosensitive composition layer to form a resist pattern; a plating step of performing a plating process on the metal layer in an area where the resist pattern is not placed; a peeling step of peeling off the resist pattern; and by the peeling step... A method for manufacturing a laminate having a conductive pattern is described, comprising a removal step of removing the exposed metal layer and forming a conductive pattern on the substrate, and a temporary support peeling step of peeling off the temporary support between the bonding step and the exposure step, or between the exposure step and the development step, wherein the photosensitive composition layer contains a resin having crosslinkable groups, the weight-average molecular weight of the resin is 3000 or more, and the mass ratio of polymerizable compounds other than the resin contained in the photosensitive composition layer to the resin is 0.85 or less. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2023-35807 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] When forming resin patterns on a substrate using a photosensitive resin composition, shape defects (e.g., drooping edges, undercuts, etc.) sometimes occurred in the resin patterns. There was a need to improve shape defects while simultaneously maintaining resolution.

[0006] One embodiment of this disclosure aims to solve the problem of providing a photosensitive resin composition that can form a resin pattern with improved shape defects and excellent resolution. Furthermore, other embodiments of this disclosure aim to solve the problems that other embodiments seek to solve: to provide a transfer film using the above-mentioned photosensitive resin composition, a method for manufacturing a resin pattern, and a method for manufacturing a conductive pattern. [Means for solving the problem]

[0007] The means for solving the above problems include the following embodiments. <1> A photosensitive resin composition comprising an alkali-soluble resin containing a crosslinkable group having a double bond, a polyfunctional (meth)acrylate, and a polymerization inhibitor. The total double bond content in the solid content of the photosensitive resin composition is 2.00 mmol / g or more relative to the total amount of solid content of the photosensitive resin composition. The proportion of double bonds based on acryloyl groups to the total number of double bonds in the solid content of the photosensitive resin composition is 10% to 50%. A photosensitive resin composition in which the molar ratio of the polymerization inhibitor content to the content of double bonds based on acryloyl groups is 0.001 to 0.015. <2> The proportion of double bonds in the alkali-soluble resin to the total number of double bonds in the solid content of the photosensitive resin composition is 20% to 40%. <1> The photosensitive resin composition described in [reference]. <3> The crosslinking group is the (meth)acryloyloxy group. <1> or <2> The photosensitive resin composition described in [reference]. <4> Polyfunctional (meth)acrylates include difunctional (meth)acrylates. <1> ~ <3> A photosensitive resin composition as described in any one of the above. <5> A temporary support, and placed on the temporary support, <1> ~ <4> A transfer film comprising a photosensitive resin layer formed from any one of the photosensitive resin compositions described in the previous article. <6> An intermediate layer is provided between the temporary support and the photosensitive resin layer. <5> The transfer film described above. <7> A thermoplastic resin layer is provided between the temporary support and the photosensitive resin layer. <5> or <6> The transfer film described above. <8> The thermoplastic resin layer contains a photobleaching compound. <7> Transfer film described above <9> <5> ~ <8> A step of bonding a transfer film and a substrate such that the photosensitive resin layer in the transfer film described in any one of the above is in contact with the substrate, A step of pattern exposure to the photosensitive resin layer after lamination, A step of heating the photosensitive resin layer after exposure, A method for manufacturing a resin pattern, comprising the steps of: developing a photosensitive resin layer after heating to form a resin pattern; and in this order. <10> In the step of heating the photosensitive resin layer after exposure, the heating temperature is 50°C to 90°C and the heating time is 20 to 80 seconds. <9> A method for manufacturing the resin pattern described above. <11> The process includes, after the step of bonding the transfer film and the substrate, and before the pattern exposure step, a step of peeling off the temporary support. <9> or <10> A method for manufacturing the resin pattern described above. <12> The step height on the surface of the photosensitive resin layer after heating is 0.1 μm or less. <9> ~ <11> A method for manufacturing a resin pattern as described in any one of the following. <13> <9> ~ <12> A step of forming a resin pattern on a substrate using a resin pattern manufacturing method described in any one of the following: A step of performing a plating process on an area of the substrate where the resin pattern is not formed, A step of removing the resin pattern, A method for manufacturing a conductive pattern, which has these steps in this order. <14> Using the method for manufacturing a resin pattern according to any one of <9> to <12>, a step of forming a resin pattern on a conductive substrate, A step of etching an area of the conductive substrate where the resin pattern is not formed, A step of removing the resin pattern, A method for manufacturing a conductive pattern, which has these steps in this order.

Advantages of the Invention

[0008] According to one embodiment of the present disclosure, a photosensitive resin composition capable of forming a resin pattern with improved shape defects and excellent resolution is provided. Also, according to another embodiment of the present disclosure, a transfer film using the photosensitive resin composition, a method for manufacturing a resin pattern, and a method for manufacturing a conductive pattern are provided.

Brief Description of the Drawings

[0009] [Figure 1] It is a schematic cross-sectional view showing an example of a transfer film according to the present disclosure.

Modes for Carrying Out the Invention

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

[0011] [Photosensitive resin composition] The photosensitive resin composition of this disclosure comprises an alkali-soluble resin containing a crosslinkable group having a double bond, a polyfunctional (meth)acrylate, and a polymerization inhibitor, wherein the total double bond content in the solids of the photosensitive resin composition is 2.00 mmol / g or more relative to the total amount of solids of the photosensitive resin composition, the proportion of double bonds based on acryloyl groups to the total number of double bonds in the solids of the photosensitive resin composition is 10% to 50%, and the molar ratio of the polymerization inhibitor content to the acryloyl group-based double bond content is 0.001 to 0.015.

[0012] As a result of diligent research by the inventors, we have found that by adopting the above configuration, shape defects can be improved and a resin pattern with excellent resolution can be formed. The mechanism by which this produces excellent effects is not clear, but it is hypothesized as follows.

[0013] When the total double bond content in the solids of the photosensitive resin composition is 2.00 mmol / g or more relative to the total amount of solids in the photosensitive resin composition, and the proportion of double bonds based on acryloyl groups to the total number of double bonds in the solids of the photosensitive resin composition is 10% to 50%, and the molar ratio of the polymerization inhibitor content to the content of double bonds based on acryloyl groups is 0.001 to 0.015, the resulting resin pattern defects (such as drooping and undercutting) are improved and the resolution is excellent. The total double bond content of 2.00 mmol / g or more suppresses swelling during the development process and improves resolution, and the proportion of double bonds based on acryloyl groups being 10% to 50% makes it easier to achieve a uniform shape.

[0014] On the other hand, Patent Document 1 does not contain any description regarding the proportion of double bonds based on acryloyl groups to the total number of double bonds in the solid content of a photosensitive resin composition being 10% to 50%.

[0015] <Alkali-soluble resin> The photosensitive resin composition of this disclosure comprises an alkali-soluble resin. In this specification, "alkaline soluble" means that the solubility of sodium carbonate in 100 g of a 1% by mass aqueous solution at 22°C is 0.1 g or more.

[0016] Alkali-soluble resins contain crosslinkable groups having double bonds.

[0017] The inclusion of crosslinkable groups in the alkali-soluble resin increases the strength of the resulting resin pattern and suppresses shape defects.

[0018] In the photosensitive resin composition of this disclosure, there are double bonds derived from crosslinkable groups contained in the alkali-soluble resin and double bonds derived from the polyfunctional (meth)acrete.

[0019] The proportion of the number of double bonds in the alkali-soluble resin to the total number of double bonds in the solid content of the photosensitive resin composition is preferably 20% to 40%, and more preferably 25% to 35%. When the above ratio is 20% or more, crosslinking points with the alkali-soluble resin are formed, suppressing swelling and improving resolution. If the above percentage is 40% or less, shape defects such as drooping hems and undercuts are less likely to occur.

[0020] The proportion of the number of double bonds in the alkali-soluble resin to the total number of double bonds in the solid content of a photosensitive resin composition is calculated using the following formula.

[0021] The percentage of double bonds in alkali-soluble resin (%) = {(Content of double bonds in alkali-soluble resin in the solid content of the photosensitive resin composition) / (Total double bond content in the solid content of the photosensitive resin composition)} × 100

[0022] The method for calculating the double bond content and the total double bond content of alkali-soluble resins will be described later.

[0023] Alkali-soluble resins preferably contain crosslinkable groups in their side chains. In this specification, "main chain" refers to the relatively longest bonding chain in the polymer compound molecule constituting the resin, and "side chain" refers to an atomic group branching off from the main chain.

[0024] From the viewpoint of curability, the crosslinkable group is preferably a radical polymerizable group having an ethylenic double bond. Examples of radical polymerizable groups include vinyl groups, vinyl ether groups, allyl groups, and (meth)acryloyloxy groups.

[0025] In particular, the crosslinkable group is preferably a (meth)acryloyloxy group.

[0026] The alkali-soluble resin preferably contains at least one structural unit that includes a crosslinkable group.

[0027] Examples of structural units containing crosslinking groups include those listed below.

[0028] [ka]

[0029] From the viewpoint of curability and the strength of the resulting resin pattern, the content of structural units containing crosslinkable groups is preferably 5% to 70% by mass, more preferably 10% to 50% by mass, and even more preferably 20% to 40% by mass, relative to the total amount of alkali-soluble resin.

[0030] One method for introducing crosslinkable groups into alkali-soluble resins is to react functional groups such as hydroxyl groups, carboxyl groups, primary amino groups, secondary amino groups, acetoacetyl groups, and sulfo groups with compounds such as epoxy compounds, blocked isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, methylol compounds, and carboxylic acid anhydrides.

[0031] A preferred method for introducing crosslinkable groups into an alkali-soluble resin is to synthesize a polymer having carboxyl groups by polymerization, and then, by polymer reaction, react a portion of the carboxyl groups of the resulting resin with glycidyl (meth)acrylate to introduce (meth)acryloyloxy groups into the polymer. This method makes it possible to obtain an alkali-soluble resin having (meth)acryloyloxy groups in its side chains.

[0032] From the viewpoint of alkali-developability, the alkali-soluble resin is preferably a (meth)acrylic resin.

[0033] In this disclosure, (meth)acrylic resin means a resin containing structural units derived from (meth)acrylic compounds.

[0034] Examples of (meth)acrylic compounds include (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamide, and (meth)acrylonitrile. Examples of (meth)acrylic acid esters include alkyl (meth)acrylates, tetrahydrofurfuryl (meth)acrylates, dimethylaminoethyl (meth)acrylates, diethylaminoethyl (meth)acrylates, glycidyl (meth)acrylates, benzyl (meth)acrylates, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, with alkyl (meth)acrylates being preferred. Examples of (meth)acrylamides include acrylamides such as diacetone acrylamide.

[0035] The alkyl group of (meth)acrylate alkyl ester may be linear or branched.

[0036] Examples of alkyl (meth)acrylates include alkyl (meth)acrylates having an alkyl group with 1 to 12 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate. The alkyl (meth)acrylate is preferably an alkyl (meth)acrylate having an alkyl group with 1 to 4 carbon atoms, and more preferably methyl (meth)acrylate or ethyl (meth)acrylate.

[0037] Alkali-soluble resins are preferably made to contain structural units having acidic groups, from the viewpoint of improving alkali developability. Examples of acidic groups include carboxyl groups, sulfo groups, phosphate groups, and phosphonic acid groups. The alkali-soluble resin more preferably contains structural units having a carboxyl group, and even more preferably contains structural units derived from (meth)acrylic acid.

[0038] When the alkali-soluble resin contains structural units having acidic groups, the content of these structural units is preferably 10% by mass or more of the total amount of the alkali-soluble resin, from the viewpoint of excellent developability. The upper limit of the content of these structural units having acidic groups is preferably 50% by mass or less, and more preferably 40% by mass or less, of the total amount of the alkali-soluble resin, from the viewpoint of excellent alkali resistance.

[0039] The alkali-soluble resin more preferably contains structural units derived from alkyl (meth)acrylate esters. When the alkali-soluble resin contains structural units derived from alkyl (meth)acrylate, the content of structural units derived from alkyl (meth)acrylate is preferably 1% to 90% by mass, more preferably 1% to 50% by mass, and even more preferably 1% to 30% by mass, based on the total amount of the alkali-soluble resin.

[0040] The alkali-soluble resin preferably contains at least one selected from the group consisting of constituent units derived from (meth)acrylic acid and constituent units derived from alkyl (meth)acrylate, and preferably contains both constituent units derived from (meth)acrylic acid and alkyl (meth)acrylate.

[0041] In particular, the alkali-soluble resin preferably contains at least one selected from the group consisting of constituent units derived from methacrylic acid and constituent units derived from alkyl methacrylate, and preferably contains both constituent units derived from methacrylic acid and constituent units derived from alkyl methacrylate.

[0042] From the viewpoint of achieving superior effects in this disclosure, the alkali-soluble resin preferably has an aromatic ring, and more preferably contains a structural unit having an aromatic ring.

[0043] Monomers that form structural units having aromatic rings include monomers having aralkyl groups, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimers, and styrene trimers). Preferred monomers for forming structural units having an aromatic ring structure are monomers having an aralkyl group or styrene. Examples of aralkyl groups include substituted or unsubstituted phenylalkyl groups and substituted or unsubstituted benzyl groups, with substituted or unsubstituted benzyl groups being preferred. Examples of monomers having a phenylalkyl group include phenylethyl (meth)acrylate. Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group [e.g., benzyl (meth)acrylate and chlorobenzyl (meth)acrylate] and vinyl monomers having a benzyl group [e.g., vinylbenzyl chloride and vinylbenzyl alcohol], with benzyl (meth)acrylate being preferred.

[0044] From the viewpoint of achieving superior effects in this disclosure, the alkali-soluble resin more preferably contains structural units derived from styrene.

[0045] When the alkali-soluble resin contains structural units having aromatic rings, the amount of structural units having aromatic rings is preferably 5% to 90% by mass, more preferably 10% to 70% by mass, and even more preferably 20% to 60% by mass, relative to the total amount of the alkali-soluble resin, from the viewpoint of achieving superior effects of this disclosure.

[0046] The alkali-soluble resin contained in the photosensitive resin composition of this disclosure may be one type or two or more types.

[0047] The alkali-soluble resin content is preferably in the range of 10% to 90% by mass, more preferably 30% to 70% by mass, and even more preferably 40% to 60% by mass, relative to the total amount of solids in the photosensitive resin composition. A ratio of 90% by mass or less of alkali-soluble resin to the photosensitive resin composition is preferable from the viewpoint of controlling the development time. On the other hand, a ratio of 10% by mass or more of alkali-soluble resin to the photosensitive resin composition is preferable from the viewpoint of improving edge fusing resistance.

[0048] 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. When Tg is 50°C or higher, the edge fusing resistance is improved. The glass transition temperature (Tg) of the alkali-soluble resin is preferably 135°C or lower, more preferably 130°C or lower, even more preferably 120°C or lower, and particularly preferably 110°C or lower. A Tg of 135°C or lower can suppress line width thickening and resolution degradation when the focal position shifts during exposure.

[0049] The Tg of alkali-soluble resins is measured by differential scanning calorimetry.

[0050] The weight-average molecular weight of the alkali-soluble resin is preferably 5,000 to 500,000. A weight-average molecular weight of 500,000 or less is preferable because it improves resolution and developability. A weight-average molecular weight of 100,000 or less is more preferable, and 60,000 or less is even more preferable. On the other hand, if the weight-average molecular weight is 5,000 or more, it is possible to control the properties of the developed aggregates, as well as the properties of the unexposed film, such as edge fusing and cut-tip properties, when used as a transfer film. The weight-average molecular weight is more preferably 10,000 or less, more preferably 20,000 or more, and particularly preferably 30,000 or more.

[0051] Edge fusing refers to the degree to which the photosensitive resin layer tends to protrude from the edge of the roll when the transfer film is wound into a roll. Cut-tip properties refer to the degree to which chips tend to fly off when the unexposed film is cut with a cutter. If these chips adhere to the upper surface of the transfer film, they will be transferred to the mask in subsequent exposure processes, causing defective products. The dispersion degree of 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. The dispersion degree is the ratio of the weight-average molecular weight to the number-average molecular weight (weight-average molecular weight / number-average molecular weight).

[0052] The photosensitive resin composition may contain resins other than alkali-soluble resins. Examples of resins other than alkali-soluble resins include acrylic resins, styrene-acrylic copolymers (provided that the styrene content is 40% by mass or less), polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0053] <Multifunctional (meth)acrylate> The photosensitive resin composition of this disclosure contains a polyfunctional (meth)acrylate.

[0054] The polyfunctional (meth)acrylate is not particularly limited as long as it is a compound having two or more (meth)acryloyloxy groups. The polyfunctional (meth)acrylate may be a difunctional (meth)acrylate or a trifunctional (meth)acrylate with three or more functions.

[0055] From the viewpoint of achieving both resolution and peelability, it is preferable that the polyfunctional (meth)acrylate includes a bifunctional (meth)acrylate.

[0056] -Compound B1- Examples of polyfunctional (meth)acrylates include bifunctional (meth)acrylates (hereinafter also referred to as "compound B1") that have at least one aromatic ring in a single molecule. From the viewpoint of resolution, it is preferable that the polyfunctional (meth)acrylate contains compound B1.

[0057] The content of compound B1 is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, and particularly preferably 60% by mass or more, based on the total amount of polyfunctional (meth)acrylate, from the viewpoint of superior resolution. There is no particular upper limit to the content of compound B1. From the viewpoint of peelability, the content of compound B1 is preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less, based on the total amount of polyfunctional (meth)acrylate.

[0058] 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 fused rings thereof. The aromatic ring in polymerizable compound B1 is preferably an aromatic hydrocarbon ring, and more preferably a benzene ring. The aromatic ring may have substituents.

[0059] Compound B1 is preferably made of a bisphenol skeleton, from the viewpoint of suppressing swelling of the photosensitive resin layer by the developer and improving resolution.

[0060] Examples of bisphenol skeletons include the bisphenol A skeleton derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), the bisphenol F skeleton derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and the bisphenol B skeleton derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane). Among these, the bisphenol A skeleton is preferred.

[0061] Examples of compounds B1 having a bisphenol skeleton include compounds having a bisphenol skeleton and two (meth)acryloyloxy groups bonded to both ends of the bisphenol skeleton.

[0062] The bisphenol skeleton and the (meth)acryloyloxy group may be directly bonded, or they may be bonded via one or more alkyleneoxy groups. The alkyleneoxy group bonded to the bisphenol skeleton is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group. The number of alkyleneoxy groups bonded to the bisphenol skeleton is not particularly limited. The number of alkyleneoxy groups bonded per molecule is preferably 4 to 16, and more preferably 6 to 14.

[0063] Compound B1 having a bisphenol skeleton is described in paragraphs 0072 to 0080 of Japanese Patent Publication No. 2016-224162, and the contents described in this publication are incorporated herein by reference.

[0064] Compound B1 is preferably a bifunctional (meth)acrylate having a bisphenol A skeleton, and more preferably 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane.

[0065] Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), and 2,2-bis(4-(methacryloxy Examples include tacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 2,2-bis(4-(methacryloylethoxy)phenyl)propane (BPE-100, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 2,2-bis(4-(acryloylethoxy)phenyl)propane (ABE-300, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and ethoxylated (10)bisphenol A diacrylate (NK ester A-BPE-10, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

[0066] Compound B1 is represented by the following formula (P1). From the viewpoint of resolution, it is preferable that compound B1 contains a compound represented by the following formula (P1).

[0067] [ka]

[0068] In formula (P1), R 21 and R 22 Each of the following independently represents either a hydrogen atom or a methyl group: A independently represents -C2H4-, B independently represents -C3H6-, n1 and n3 independently represent integers from 1 to 39, and n1+n3 is an integer from 2 to 40, and n2 and n4 independently represent integers from 0 to 29, and n2+n4 is an integer from 0 to 30. The sequence of the repeating units -(AO)- and -(BO)- may be random or blocky. If the sequence is blocky, either -(AO)- or -(BO)- may be on the bisphenyl group side.

[0069] n1+n2+n3+n4 is preferably between 2 and 20, more preferably between 2 and 16, and even more preferably between 2 and 8.

[0070] Furthermore, n2+n4 is preferably between 0 and 10, more preferably between 0 and 4, even more preferably between 0 and 2, and particularly preferably 0.

[0071] The compound B1 contained in the photosensitive resin composition may be one type or two or more types.

[0072] The content of compound B1 is preferably 10% by mass or more, and more preferably 20% by mass or more, relative to the solid content of the photosensitive resin composition, from the viewpoint of superior resolution. There is no particular upper limit on the content of polymerizable compound B1. From the viewpoint of improving transferability and edge fusing resistance, the content of compound B1 is preferably 70% by mass or less, and more preferably 60% by mass or less.

[0073] -Compound B2- Examples of polyfunctional (meth)acrylates include difunctional (meth)acrylates that do not have an aromatic ring (hereinafter also referred to as "compound B2").

[0074] Examples of compound B2 include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate.

[0075] Examples of alkylene glycol di(meth)acrylates include tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate.

[0076] 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.

[0077] Examples of urethane di(meth)acrylates include propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Examples of commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

[0078] -Compound B3- Examples of polyfunctional (meth)acrylates include (meth)acrylates with three or more functions (hereinafter also referred to as "compound B").

[0079] Examples of compound B3 include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanurate tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified products thereof.

[0080] Here, "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, while "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0081] Examples of alkylene oxide-modified (meth)acrylates with three or more functionalities include caprolactone-modified (meth)acrylate compounds (KAYARAD® DPCA-20, manufactured by Nippon Kayaku Co., Ltd.; A-9300-1CL, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040, manufactured by Nippon Kayaku Co., Ltd.; ATM-35E and A-9300, manufactured by Shin Nakamura Chemical Industry Co., Ltd.; EBECRYL® 135, manufactured by Daicel Ornex Co., Ltd.), ethoxylated glycerin triacrylate (A-GLY-9E, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), Arronix® TO-2349 (manufactured by Toagosei Co., Ltd.), Arronix M-520 (manufactured by Toagosei Co., Ltd.), and Arronix M-510 (manufactured by Toagosei Co., Ltd.).

[0082] The photosensitive resin composition may contain other polymerizable compounds besides polyfunctional (meth)acrylates. Other polymerizable compounds are not particularly limited and can be appropriately selected from conventionally known compounds. Examples of other polymerizable compounds include compounds having one ethylenically unsaturated group in one molecule (i.e., monofunctional ethylenically unsaturated compounds).

[0083] Furthermore, other polymerizable compounds may be polymerizable compounds having an acid group as described in paragraphs 0025 to 0030 of Japanese Patent Publication No. 2004-239942.

[0084] Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0085] The photosensitive resin composition preferably contains 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.

[0086] The polyfunctional (meth)acrylate content is preferably 10% to 70% by mass, more preferably 20% to 60% by mass, and even more preferably 20% to 50% by mass, based on the total amount of solids in the photosensitive resin composition.

[0087] <Photopolymerization initiator> The photosensitive resin composition of this disclosure preferably contains a photopolymerization initiator.

[0088] A photopolymerization initiator is a compound that initiates the polymerization of a polymerizable compound when exposed to active light such as ultraviolet light, visible light, or X-rays. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used.

[0089] Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators. Among these, photoradical polymerization initiators are preferred.

[0090] Examples of photoradical polymerization initiators include photopolymerization initiators having an oxime ester skeleton, photopolymerization initiators having an α-aminoalkylphenone skeleton, photopolymerization initiators having an α-hydroxyalkylphenone skeleton, photopolymerization initiators having an acylphosphine oxide skeleton, and photopolymerization initiators having an N-phenylglycine skeleton.

[0091] Furthermore, from the viewpoint of photosensitivity, visibility of exposed and unexposed areas, and resolution, the photosensitive resin composition preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and their derivatives as a photoradical polymerization initiator. The two 2,4,5-triarylimidazole skeletons in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different. Examples of derivatives of the 2,4,5-triarylimidazole dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0092] The photoradical polymerization initiator may be the polymerization initiator described in paragraphs 0031 to 0042 of Japanese Patent Publication No. 2011-95716 and paragraphs 0064 to 0081 of Japanese Patent Publication No. 2015-14783.

[0093] Examples of photoradical polymerization initiators include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), and benzophenone.

[0094] Examples of commercially available photoradical polymerization initiators include 2,4-bis(trichloromethyl)-6-[2-(4-methylphenyl)ethenyl]-1,3,5-triazine (product name: TAZ-110, manufactured by Midori Chemical Co., Ltd.), (product name: TAZ-111, manufactured by Midori Chemical Co., Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyl oxime) (product name: Irgacure® OXE-01, manufactured by BASF Japan), and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyl oxime) (product name: Irgacure OXE-02 (manufactured by BASF Japan), Irgacure OXE-03 (manufactured by BASF Japan), OXE-04 (manufactured by BASF Japan), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (product name: Omnirad 379EG, manufactured by IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (product name: Omnirad 907, manufactured by IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (product name: Omnirad 127, manufactured by IGM Resins (Manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (Trade name: Omnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Trade name: Omnirad 1173, manufactured by IGM Resins BV), 1-hydroxycyclohexylphenyl ketone (Trade name: Omnirad 184, manufactured by IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethane-1-one (Trade name: Omnirad 651, manufactured by IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Trade name: Omnirad TPO H, manufactured by IGM Resins BV)Examples include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins BV), oxime ester-based photopolymerization initiators (trade name: Lunar 6, manufactured by DKSH Japan Co., Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by Hampford), and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.).

[0095] A photocationic polymerization initiator (photoacid generator) is a compound that generates acid upon receiving active light. While the photocationic polymerization initiator is not particularly limited, it is preferable that it is a compound that reacts to active light with a wavelength of 300 nm or higher, preferably 300 nm to 450 nm, and generates acid. Furthermore, even compounds that do not directly react to active light with a wavelength of 300 nm or higher can be preferably used in combination with a sensitizer if they react to such light and generate acid when used in combination with a sensitizer.

[0096] The photocationic polymerization initiator is preferably one that generates an acid with a pKa of 4 or less, more preferably one that generates an acid with a pKa of 3 or less, and particularly preferably one that generates an acid with a pKa of 2 or less. The lower limit of the pKa is not particularly limited, for example, -10.0 is preferred.

[0097] Examples of photocationic polymerization initiators include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators.

[0098] Examples of ionic photocationic polymerization initiators include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.

[0099] The ionic photocationic polymerization initiator may be the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of Japanese Patent Application Publication No. 2014-85643.

[0100] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazine compounds, diazomethane compounds, imidosulfonate compounds, and oximesulfonate compounds. The trichloromethyl-s-triazine compounds, diazomethane compounds, and imidosulfonate compounds may be those described in paragraphs 0083 to 0088 of Japanese Patent Publication No. 2011-221494. The oximesulfonate compounds may be those described in paragraphs 0084 to 0088 of International Publication No. 2018 / 179640.

[0101] The photopolymerization initiator contained in the photosensitive resin composition may be one type or two or more types.

[0102] The content of the photopolymerization initiator is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 3% by mass or more, relative to the solid content of the photosensitive resin composition. The upper limit of the photopolymerization initiator content is not particularly limited. The content of the photopolymerization initiator is preferably 10% by mass or less, and more preferably 8% by mass or less, relative to the solid content of the photosensitive resin composition.

[0103] <Sensitizer> The photosensitive resin composition of this disclosure may contain a sensitizer.

[0104] The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used. Examples of sensitizers include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

[0105] The photosensitive resin composition may contain only one type of sensitizer, or two or more types.

[0106] When a photosensitive resin composition contains a sensitizer, the amount of sensitizer can be appropriately selected depending on the purpose. From the viewpoint of improving sensitivity to light sources and improving curing speed by balancing polymerization rate and chain transfer, the amount of sensitizer is preferably 0.01% to 5% by mass, and more preferably 0.05% to 1% by mass, relative to the solid content of the photosensitive resin composition.

[0107] <Polymerization inhibitor> The photosensitive resin composition of this disclosure contains a polymerization inhibitor.

[0108] Examples of polymerization inhibitors include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. Other examples of polymerization inhibitors include phenothiazine, phenoxazine, 4-methoxyphenol, naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. Among these, the radical polymerization inhibitor is preferably phenothiazine, phenoxazine, 4-methoxyphenol, or nitrosophenylhydroxyamine aluminum salt.

[0109] If the photosensitive resin composition contains a polymerization inhibitor, the amount of polymerization inhibitor is preferably 0.01% to 5% by mass, and more preferably 0.05% to 1% by mass, relative to the solid content of the photosensitive resin composition, from the viewpoint of storage stability of the photosensitive resin composition.

[0110] In the photosensitive resin composition of this disclosure, the molar ratio of the polymerization inhibitor content to the content of double bonds based on acryloyl groups is 0.001 to 0.015. When the above molar ratio is 0.001 or higher, the reaction by diffusion of growth monomers having acryloyl groups proceeds uniformly, improving the shape and resolution of the resin pattern. When the above molar ratio is 0.015 or less, the diffusion of growth monomers having acryloyl groups between the exposed and unexposed areas can be controlled, improving resolution.

[0111] From the above viewpoint, a molar ratio of 0.001 to 0.010 is more preferable. The content of double bonds based on acryloyl groups is calculated using the same method as the method for calculating the total double bond content in the solid content of a photosensitive resin composition.

[0112] <Antioxidant> The photosensitive resin composition of this disclosure may contain an antioxidant.

[0113] Examples of antioxidants include 3-pyrazolidones such as 1-phenyl-3-pyrazolidone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorhydroquinone; and paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine. In particular, 3-pyrazolidones are preferred as antioxidants, and 1-phenyl-3-pyrazolidone is more preferred, as they exhibit superior effects in this disclosure.

[0114] When the photosensitive resin composition contains an antioxidant, the antioxidant content is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more, relative to the solid content of the photosensitive resin composition. There is no particular upper limit to the antioxidant content, but 1% by mass or less is preferred.

[0115] <Chain movement agent> The photosensitive resin composition of this disclosure may contain a chain transfer agent.

[0116] Examples of chain transfer agents include N-phenylcarbamoylmethyl-N-carboxymethylaniline and N,N-tetraethyl-4,4-diaminobenzophenone.

[0117] When the photosensitive resin composition contains a chain transfer agent, the antioxidant content is preferably 0.01% to 5% by mass, and more preferably 0.05% to 1% by mass, relative to the solid content of the photosensitive resin composition.

[0118] <Dye> The photosensitive resin composition of this disclosure may contain a dye. The photosensitive resin composition of this disclosure preferably contains a dye (hereinafter also simply referred to as "dye N") whose maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development is 450 nm or more, and whose maximum absorption wavelength changes with the presence of an acid, base, or radical, from the viewpoint of visibility of the exposed and unexposed areas, pattern visibility after development, and resolution. When dye N is included, although the detailed mechanism is unknown, adhesion to adjacent layers (e.g., temporary support and intermediate layer) is improved and resolution is further enhanced.

[0119] In this specification, the phrase "the maximum absorption wavelength of a dye changes due to an acid, base, or radical" may mean any of the following: a dye in a colored state becomes decolorized due to an acid, base, or radical; a dye in a decolorized state becomes colored due to an acid, base, or radical; or a dye in a colored state changes to a colored state of another hue.

[0120] Specifically, the dye may be a compound that changes from a decolorized state to a colored state upon exposure, or a compound that changes from a colored state to a decolorized state upon exposure. In this case, the dye may change its colored or decolorized state due to the generation of acids, bases, or radicals within the photosensitive resin layer upon exposure, or the dye may change its colored or decolorized state due to a change in the state (e.g., pH) within the photosensitive resin layer caused by acids, bases, or radicals. Furthermore, dye N may be a dye that does not undergo exposure but changes its colored or decolorized state upon direct stimulation by acids, bases, or radicals.

[0121] In particular, from the viewpoint of visibility of exposed and unexposed areas, as well as resolution, the dye is preferably one whose maximum absorption wavelength changes with acid or radicals, and more preferably one whose maximum absorption wavelength changes with radicals.

[0122] From the viewpoint of visibility of the exposed and unexposed areas, as well as resolution, the photosensitive resin composition preferably contains both a dye N whose maximum absorption wavelength changes due to radicals, and a photoradical polymerization initiator.

[0123] Furthermore, from the viewpoint of visibility between the exposed and unexposed areas, the dye is preferably a dye that develops color in response to an acid, base, or radical.

[0124] An example of a dye color development mechanism is a method in which a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photobase generator is added to a photosensitive resin composition, and after exposure, the radicals, acids, or bases generated from the photoradical polymerization initiator, photocationic polymerization initiator, or photobase generator cause color development.

[0125] From the viewpoint of visibility of the exposed and unexposed areas, the maximum absorption wavelength of the dye in the wavelength range of 400 nm to 780 nm during color development is preferably 550 nm or higher, more preferably 550 nm to 700 nm, and even more preferably 550 nm to 650 nm.

[0126] Furthermore, a dye may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development, or it may have two or more. If dye N has two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm during color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths should be 450 nm or higher.

[0127] The maximum absorption wavelength of a dye is obtained by measuring the transmission spectrum of a solution containing the dye (at a temperature of 25°C) in the range of 400 nm to 780 nm using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) in an atmospheric environment, and detecting the wavelength at which the light intensity is minimum (i.e., the maximum absorption wavelength).

[0128] Examples of dyes that develop or decolorize upon exposure include leuco compounds. Examples of dyes that decolorize upon exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. Among these, leuco compounds are preferred as the dye from the viewpoint of visibility between the exposed and unexposed areas.

[0129] Examples of leuco compounds include leuco compounds having a triarylmethane skeleton (triarylmethane dyes), leuco compounds having a spiropyran skeleton (spiropyran dyes), leuco compounds having a fluorane skeleton (fluorane dyes), leuco compounds having a diarylmethane skeleton (diarylmethane dyes), leuco compounds having a rhodamine lactam skeleton (rhodamine lactam dyes), leuco compounds having an indolylphthalide skeleton (indolylphthalide dyes), and leuco compounds having a leucoauramine skeleton (leucoauramine dyes).

[0130] In particular, the leuco compound is preferably a triarylmethane-based dye or a fluorane-based dye, and more preferably a leuco compound (triphenylmethane-based dye) or fluorane-based dye having a triphenylmethane skeleton.

[0131] From the viewpoint of visibility between the exposed and unexposed areas, the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring. The lactone ring, sultine ring, or sultone ring of the leuco compound reacts with radicals generated from a photoradical polymerization initiator or acids generated from a photocationic polymerization initiator to change from a closed ring state to an open ring state and develop color, or to change from an open ring state to a closed ring state and decolorize. The leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring and develops color upon ring opening by a radical or acid, and more preferably has a lactone ring and develops color upon ring opening by a radical or acid.

[0132] Examples of pigments include the following dyes and leuco compounds. The dyes include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuchsine, Methyl Violet 2B, Quinaldine Red, Rose Bengal, Methanyl Yellow, Thymol Sulfonphthalein, Xylenol Blue, Methyl Orange, Paramethyl Red, Congo Red, Benzopulpurine 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsine, Victoria Pure Blue - Naphthalene Sulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Co., Ltd.) Examples include: Oil Red OG (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industry Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (manufactured by Hodogaya Chemical Industry Co., Ltd.), m-Cresol Purple, Cresol Red, Rhodamine B, Rhodamine 6G, Sulforhodamine B, Auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-pN,N-bis(hydroxyethyl)aminophenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0133] Examples of leuco compounds include p,p',p''-hexamethyltriaminotriphenylmethane (leucocrystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoylleucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, and 3-(N-cyclohexyl-N-methylamino)-6 -Methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluorane, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N-diethylamino) (Tylamino)-7-benzylaminofluorane, 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6-methyl-7-xylidinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl-2-methylindole-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindole-3-yl)phthalide Examples include cylindole-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-zaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthene-3-one.

[0134] From the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, the dye is preferably a dye whose maximum absorption wavelength changes due to radicals, and more preferably a dye that develops color due to radicals.

[0135] The dye is preferably Leucocrystal violet, crystal violet lactone, brilliant green, or Victoria pure blue naphthalene sulfonate.

[0136] From the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, the dye content is preferably 0.1% by mass or more, more preferably 0.1% to 10% by mass, even more preferably 0.1% to 5% by mass, and particularly preferably 0.1% to 1% by mass, relative to the solid content of the photosensitive resin composition.

[0137] <Surfactants> The photosensitive resin composition of this disclosure may contain a surfactant from the viewpoint of uniform thickness.

[0138] Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. Among these, nonionic surfactants are preferred.

[0139] Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based nonionic surfactants, and fluorine-based nonionic surfactants.

[0140] From the viewpoint of improving resolution, the photosensitive resin composition preferably contains a fluorine-based nonionic surfactant. This is because the inclusion of a fluorine-based nonionic surfactant in the photosensitive resin composition is thought to suppress the penetration of the etching solution into the photosensitive resin layer, thereby reducing side etching.

[0141] Examples of commercially available fluorine-based nonionic surfactants include Megafac F-551, F-552, and F-554 (all manufactured by DIC Corporation).

[0142] <Solvent> The photosensitive resin composition of this disclosure preferably contains a solvent. When the photosensitive resin composition of this disclosure contains a solvent, the formation of a photosensitive resin layer by coating tends to become easier.

[0143] 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.

[0144] When preparing a transfer film comprising a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer, the photosensitive resin composition preferably contains at least one selected from the group consisting of alkylene glycol ethers and alkylene glycol ether acetates. In particular, the solvent is more preferably a mixed solvent containing at least one selected from the group consisting of alkylene glycol ethers and alkylene glycol ether acetate solvents, and at least one selected from the group consisting of ketones and cyclic ethers, and even more preferably a mixed solvent containing at least one selected from the group consisting of alkylene glycol ethers and alkylene glycol ether acetates, a ketone, and a cyclic ether.

[0145] Examples of alkylene glycol ethers include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.

[0146] 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.

[0147] The solvent may be one of the solvents described in paragraphs 0092-0094 of International Publication No. 2018 / 179640 and one of the solvents described in paragraph 0014 of Japanese Patent Application Publication No. 2018-177889, the contents of which are incorporated herein by reference.

[0148] The photosensitive resin composition may contain only one solvent or two or more solvents. The solvent content is preferably 50 to 1,900 parts by mass, and more preferably 100 to 900 parts by mass, per 100 parts by mass of solids of the photosensitive resin composition.

[0149] <Other ingredients> The photosensitive resin composition of this disclosure may further contain known additives such as metal oxide particles, dispersants, acid builders, development accelerators, conductive fibers, thermoacid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic precipitation inhibitors.

[0150] The method for preparing the photosensitive resin composition is not particularly limited. For example, one method involves preparing a solution in which each component is dissolved in the solvent, and then mixing the resulting solutions in predetermined proportions.

[0151] <Double bond content> In the photosensitive resin composition of this disclosure, the total double bond content in the solid content of the photosensitive resin composition is 2.00 mmol / g or more relative to the total amount of solid content of the photosensitive resin composition. When the total double bond content is 2.00 mmol / g or higher, the resulting resin pattern has a superior shape. 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. From the viewpoint of resist exfoliation, the total double bond content is preferably 3.50 mmol / g or less, and more preferably 3.00 mmol / g or less.

[0152] The total double bond content mentioned above can be calculated as the sum of the double bond content of compounds containing double bonds that are included in the solid content of the photosensitive resin composition.

[0153] If the photosensitive resin composition of this disclosure 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.

[0154] If a compound containing a double bond is a compound that does not have structural units, the double bond content can be calculated by the following method. Double bond content = (Content of compound containing double bonds relative to the solid content of the photosensitive resin composition) × (Number of double bonds in the compound containing double bonds) / (Molecular weight of the compound containing double bonds)

[0155] If a compound containing a double bond is a compound that has a double bond in its structural unit, the double bond content can be calculated using the following method. In the formula below, "MD" represents a structural unit containing a double bond. Double bond content = (Content of compound containing double bonds relative to the solid content of the photosensitive resin composition) × (Content of MD relative to the total amount of compound containing double bonds) × (Number of double bonds in MD) / (Molecular weight of MD)

[0156] The double bond content can be adjusted by the type and amount of alkali-soluble resin and polyfunctional (meth)acrete.

[0157] From the viewpoint of resolution, the double bond content of the alkali-soluble resin is preferably 0.30 mmol / g to 1.50 mmol / g, and more preferably 0.70 mmol / g to 1.20 mmol / g, relative to the total amount of solids in the photosensitive resin composition. Furthermore, from the viewpoint of resolution and pattern shape, the double bond content of the polyfunctional (meth)acrete is preferably 0.80 mmol / g to 2.00 mmol / g, and more preferably 1.00 mmol / g to 1.80 mmol / g, relative to the total amount of solids in the photosensitive resin composition.

[0158] <Number of double bonds based on acryloyl group> In the photosensitive resin composition of this disclosure, the proportion of double bonds based on acryloyl groups to the total number of double bonds in the solid content of the photosensitive resin composition is 10% to 50%. When the proportion of double bonds based on the acryloyl group is 10% or more, the diffusivity of the growing monomer during polymerization is improved, and the shape of the resin pattern becomes more uniform. Furthermore, if the proportion of double bonds based on the acryloyl group is 50% or less, the resolution is excellent. From the above viewpoint, it is preferable that the proportion of double bonds based on the acryloyl group is 10% to 50%.

[0159] The proportion of double bonds based on the acryloyl group is calculated using the following method. First, the content of double bonds based on acryloyl groups is calculated using the same method as for calculating the total double bond content in the solid content of the photosensitive resin composition. Next, the proportion of double bonds based on the acryloyl group is calculated based on the following formula. Percentage of double bonds based on acryloyl groups (%) = {(Content of double bonds based on acryloyl groups) / (Total content of double bonds)} × 100

[0160] [Transfer film] The transfer film of this disclosure includes a temporary support and a photosensitive resin layer disposed on the temporary support and formed from the photosensitive resin composition. The photosensitive resin layer formed from the photosensitive resin composition may be a photosensitive resin layer containing solid components of the photosensitive resin composition.

[0161] The following describes a specific embodiment of the transfer film.

[0162] The transfer film 20 shown in Figure 1 comprises, in this order, a temporary support 11, a transfer layer 12 including a thermoplastic resin layer 13, an intermediate layer 15, and a photosensitive resin layer 17, and a protective film 19.

[0163] Although the transfer film 20 shown in Figure 1 has a protective film 19 placed on it, the protective film 19 does not necessarily have to be placed on it.

[0164] Furthermore, although the transfer film 20 shown in Figure 1 has a thermoplastic resin layer 13 and an intermediate layer 15 arranged therein, the thermoplastic resin layer 13 or the intermediate layer 15, or the thermoplastic resin layer 13 and the intermediate layer 15, may not be arranged.

[0165] The following describes each element that makes up the transfer film.

[0166] <Provisional support> The temporary support is a removable support that supports the photosensitive resin layer.

[0167] The temporary support may be a single layer or a laminate consisting of two or more layers stacked together. Examples of temporary supports include those consisting only of a substrate; a laminate comprising a substrate and a particle-containing layer disposed on one side of the substrate; and a laminate comprising a substrate and particle-containing layers disposed on both sides of the substrate.

[0168] Examples of substrates that constitute the temporary support include glass, resin film, and paper. From the viewpoint of strength, flexibility, and light transmittance, the substrate constituting the temporary support is preferably a resin film.

[0169] Examples of resin films include polyethylene terephthalate (PET) film, cellulose triacetate film, polystyrene film, and polycarbonate film. Among these, the resin film is preferably a PET film, and more preferably a biaxially oriented PET film.

[0170] If a particle-containing layer is arranged on one or both sides of the substrate, the particle-containing layer may be one layer or two or more layers.

[0171] The particle-containing layer is formed, for example, by applying a particle-containing layer composition to a substrate and drying it. Alternatively, the particle-containing layer can be formed by co-extrusion during the formation of a resin film. The particle-containing layer composition preferably contains a binder polymer and particles. The type of binder polymer is not particularly limited and can be appropriately selected depending on the purpose. Examples of binder polymers include acrylic resins, urethane resins, olefin resins, styrene-butadiene resins, ester resins, vinyl chloride resins, and vinylidene chloride resins. When forming the particle-containing layer by co-extrusion, PET is preferably used as the binder polymer.

[0172] The particle-containing layer may contain one type of binder polymer and one type of particle, or it may contain two or more types.

[0173] The particles contained in the particle-containing layer are not particularly limited and can be appropriately selected depending on the purpose. The particle content in the particle-containing layer can be appropriately adjusted by the amount of particles added to the particle-containing layer composition. In this specification, the particles contained in the particle-containing layer are referred to as "added particles".

[0174] The added particles are distinct from impurities that are unexpectedly introduced during the manufacturing process of the temporary support, and from particles that are formed during the manufacturing process of the temporary support. Preferably, the added particles are those that do not melt at 200°C.

[0175] In a temporary support, whether or not a particle is an added particle can be determined, for example, by the following method. Added particles usually have uniform shape and distribution, so they can be identified by observation with an optical microscope.

[0176] Examples of added particles include inorganic particles and organic particles.

[0177] Examples of inorganic particles include inorganic oxide particles such as silicon dioxide (silica), titanium dioxide (titania), zirconium oxide (zirconia), magnesium oxide (magnesia), and aluminum oxide (alumina).

[0178] Examples of organic particles include acrylic resin, polyester, polyurethane, and polycarbonate. Examples include polymer particles such as nates, polyolefins, and polystyrene.

[0179] If the temporary support has a particle-containing layer, it is preferable that the added particles contained in the particle-containing layer are inorganic oxide particles.

[0180] The average particle size of the added particles is not particularly limited, but is, for example, 0.1 μm to 10 μm. The average particle size is measured using a TEM (transmission electron microscope) after cutting a 100 nm thick section with an ultramicrotome.

[0181] The thickness of the temporary support is preferably 25 μm or more, more preferably 50 μm or more, and even more preferably 75 μm or more, from the viewpoint of suppressing deformation of the circuit board to be bonded with the transfer film. The upper limit of the thickness is not particularly limited, for example, 200 μm.

[0182] The temporary support may be made from recycled materials. Examples of recycled materials include used film, which has been washed, chipped, and then used as raw material to make film. A specific example of recycled materials is Toray's Ecouse series.

[0183] <Photosensitive resin layer> The photosensitive resin layer is formed from the photosensitive resin composition of this disclosure. The photosensitive resin layer preferably contains the solid content of the photosensitive resin composition of this disclosure. If the photosensitive resin composition contains a solvent, the photosensitive resin layer in the transfer film contains at least components other than the solvent of the photosensitive resin composition (i.e., solids). In this case, the photosensitive resin layer may further contain the solvent. An example of a case where the photosensitive resin layer contains a solvent is when a photosensitive resin composition containing a solvent is applied and dried to form a photosensitive resin layer, and the solvent remains in the photosensitive resin layer even after drying.

[0184] The photosensitive resin layer is preferably a negative-type photosensitive resin layer in which the solubility of the exposed area in the developer decreases upon exposure, and the unexposed area is removed by development.

[0185] The average thickness of the photosensitive resin layer is preferably 0.5 μm to 30 μm, more preferably 1 μm to 10 μm, and even more preferably 1 μm to 5 μm, from the viewpoint of pattern shape, surface roughness, and resolution.

[0186] <Middle class> The transfer film preferably includes an intermediate layer between the temporary support and the photosensitive resin layer.

[0187] By incorporating an intermediate layer, mixing of components can be suppressed when applying multiple layer-forming compositions and during storage after application.

[0188] The intermediate layer is preferably a water-soluble resin layer containing a water-soluble resin. Furthermore, as an intermediate layer, an oxygen-blocking layer with oxygen-blocking function, as described as a "separation layer" in Japanese Patent Publication No. 5-072724, can also be used. Using an oxygen-blocking layer as the intermediate layer is preferable because it improves sensitivity during exposure, reduces the time load on the exposure machine, and improves productivity.

[0189] The oxygen barrier layer used as the intermediate layer may be appropriately selected from known layers described in the above publications, etc. Among these, an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22°C) is preferred.

[0190] The following describes the various components that the intermediate layer may contain.

[0191] The intermediate layer preferably contains a resin.

[0192] The above resin preferably contains a water-soluble resin as part or all of it.

[0193] Examples of resins that can be used as water-soluble resins include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof.

[0194] Furthermore, as the water-soluble resin, copolymers of (meth)acrylic acid / vinyl compounds can also be used. Among the copolymers of (meth)acrylic acid / vinyl compounds, copolymers of (meth)acrylic acid / (meth)acrylate are preferred, and copolymers of methacrylic acid / methacrylate are more preferred.

[0195] When the water-soluble resin is a copolymer of (meth)acrylic acid / vinyl compound, the composition ratio (mol%) is preferably, for example, 90 / 10 to 20 / 80, and more preferably 80 / 20 to 30 / 70.

[0196] The lower limit of the weight-average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more. The upper limit is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less. The dispersion degree (Mw / Mn) of the water-soluble resin is preferably 1 to 10, and more preferably 1 to 5.

[0197] Furthermore, in order to further improve the ability to suppress interlayer mixing of the intermediate layer, it is preferable that the resin contained in the intermediate layer is different from the resin contained in the layer located on one side of the intermediate layer and the resin contained in the layer located on the other side. For example, if an alkali-soluble resin is contained in the photosensitive resin layer and a thermoplastic resin (alkali-soluble resin) is contained in the thermoplastic resin layer described later, it is preferable that the resin contained in the intermediate layer is different from the alkali-soluble resin and the thermoplastic resin (alkali-soluble resin) contained in the photosensitive resin layer.

[0198] The water-soluble resin preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone, in order to further improve oxygen barrier properties and interlayer mixing inhibition ability.

[0199] The water-soluble resin contained in the intermediate layer may be one type or two or more types.

[0200] The content of the water-soluble resin is not particularly limited, but in terms of further improving oxygen barrier properties and interlayer mixing suppression ability, it is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the water-soluble resin layer (intermediate layer). There is no particular upper limit, but for example, it is preferably 99.9% by mass or less, and even more preferably 99.8% by mass or less.

[0201] The intermediate layer may contain known additives such as surfactants, as needed.

[0202] The thickness of the intermediate layer is not particularly limited, but is preferably 0.1 μm to 5 μm, and more preferably 0.5 to 3 μm. When the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the oxygen barrier properties are not reduced, and the ability to suppress interlayer mixing is excellent. Furthermore, the increase in the time required to remove the intermediate layer during development can also be suppressed.

[0203] <Thermoplastic resin layer> The transfer film preferably includes a thermoplastic resin layer between the temporary support and the photosensitive resin layer. Furthermore, it is preferable that the transfer film includes a thermoplastic resin layer between the temporary support and the intermediate layer. The inclusion of a thermoplastic resin layer in the transfer film improves its conformability to the substrate during the lamination process, suppressing the inclusion of air bubbles between the substrate and the transfer film. As a result, adhesion between the thermoplastic resin layer and adjacent layers (e.g., the temporary support) can be ensured.

[0204] The thermoplastic resin layer contains a resin. The resin contains a thermoplastic resin as part or all of it. In other words, in one embodiment, it is preferable that the resin of the thermoplastic resin layer is a thermoplastic resin.

[0205] (Alkali-soluble resin (thermoplastic resin)) The thermoplastic resin is preferably an alkali-soluble resin.

[0206] Examples of alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0207] As the alkali-soluble resin, acrylic resin is preferred from the viewpoint of developability and adhesion to adjacent layers.

[0208] Here, acrylic resin means a resin having at least one constituent unit selected from the group consisting of constituent units derived from (meth)acrylic acid, constituent units derived from (meth)acrylic acid esters, and constituent units derived from (meth)acrylamide.

[0209] Preferably, the acrylic resin contains a total content of 50% by mass or more of constituent units derived from (meth)acrylic acid, (meth)acrylic acid ester, and (meth)acrylamide, relative to the total mass of the acrylic resin.

[0210] In particular, the total content of constituent units derived from (meth)acrylic acid and constituent units derived from (meth)acrylic acid esters is preferably 30% to 100% by mass, and more preferably 50% to 100% by mass, relative to the total mass of the acrylic resin.

[0211] Furthermore, the alkali-soluble resin is preferably a polymer having acidic groups.

[0212] Examples of acidic groups include carboxyl groups, sulfol groups, phosphate groups, and phosphonic acid groups, with carboxyl groups being preferred.

[0213] From the viewpoint of developability, alkali-soluble resins with an acid value of 60 mg KOH / g or higher are more preferred, and carboxyl group-containing acrylic resins with an acid value of 60 mg KOH / g or higher are even more preferred.

[0214] The upper limit of the acid value of the alkali-soluble resin is not particularly limited, but it is preferably 300 mg KOH / g or less, more preferably 250 mg KOH / g or less, even more preferably 200 mg KOH / g or less, and particularly preferably 150 mg KOH / g or less.

[0215] The carboxyl group-containing acrylic resin with an acid value of 60 mgKOH / g or higher is not particularly limited and can be appropriately selected from known resins.

[0216] For example, examples include an alkali-soluble resin which is a carboxyl group-containing acrylic resin with an acid value of 60 mg KOH / g or more among the polymers described in paragraph

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

[0033] to

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

[0053] to

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

[0217] The copolymerization ratio of the carboxyl group-containing structural units in the above-mentioned carboxyl group-containing acrylic resin is preferably 5% to 50% by mass, more preferably 10% to 40% by mass, and even more preferably 12% to 30% by mass, based on the total mass of the acrylic resin.

[0218] As for the alkali-soluble resin, an acrylic resin having constituent units derived from (meth)acrylic acid is particularly preferred from the viewpoint of developability and adhesion to adjacent layers.

[0219] Alkali-soluble resins may have reactive groups. Reactive groups can be any groups capable of addition polymerization, including ethylenically unsaturated groups; polycondensable groups such as hydroxyl and carboxyl groups; and polyaddition reactive groups such as epoxy groups and (blocked) isocyanate groups.

[0220] 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.

[0221] The alkali-soluble resin contained in the thermoplastic resin layer may be one type or two or more types.

[0222] From the viewpoint of developability and adhesion to adjacent layers, the content of alkali-soluble resin is preferably 10% to 99% by mass, more preferably 20% to 90% by mass, even more preferably 40% to 80% by mass, and particularly preferably 50% to 75% by mass, based on the total mass of the thermoplastic resin layer.

[0223] (dye) The thermoplastic resin layer preferably contains a dye (also simply called "dye B") whose maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development is 450 nm or higher, and whose maximum absorption wavelength changes with the presence of an acid, base, or radical.

[0224] A preferred embodiment of dye B is the same as that of the preferred embodiment of dye N described above, except for the points described later.

[0225] From the viewpoint of visibility and resolution of exposed and unexposed areas, dye B is preferably a dye whose maximum absorption wavelength changes with acid or radicals, and more preferably a dye whose maximum absorption wavelength changes with acid.

[0226] From the viewpoint of visibility and resolution of the exposed and unexposed areas, the thermoplastic resin layer preferably contains both a dye whose maximum absorption wavelength changes with an acid as dye B, and a compound that generates an acid when exposed to light, as described later.

[0227] The dye B contained in the thermoplastic resin layer may be one type or two or more types.

[0228] From the viewpoint of visibility of the exposed and unexposed areas, the content of dye B is preferably 0.2% by mass or more, more preferably 0.2% to 6% by mass, even more preferably 0.2% to 5% by mass, and particularly preferably 0.25% to 3.0% by mass, relative to the total mass of the thermoplastic resin layer.

[0229] Here, the content of pigment B refers to the amount of pigment B present in the thermoplastic resin layer when all of the pigment B is in a colored state. Below, we will explain how to quantify the content of pigment B using a pigment that develops color through radicals as an example. Solutions were prepared by dissolving 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone. To each of the resulting solutions, the photoradical polymerization initiator Irgacure OXE01 (trade name, BASF Japan Ltd.) was added, and radicals were generated by irradiating with 365 nm light, causing all the dyes to develop color. Subsequently, under an atmospheric environment, the absorbance of each solution at a liquid temperature of 25°C was measured using a spectrophotometer (UV3100, Shimadzu Corporation), and a calibration curve was created. Next, the absorbance of the solution in which all of the dye has developed is measured, using the same method as above, except that 0.1 g of the thermoplastic resin layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of dye contained in the thermoplastic resin layer is calculated based on the calibration curve. Note that 3g of the thermoplastic resin layer is equivalent to 3g of the solid content of the composition for forming the thermoplastic resin layer.

[0230] (Compounds that generate acids, bases, or radicals upon exposure to light) The thermoplastic resin layer may contain a compound (also simply called "compound C") that generates an acid, base, or radical upon exposure to light.

[0231] As compound C, a compound that generates an acid, base, or radical upon exposure to active light such as ultraviolet light and visible light is preferred.

[0232] As the compound C, known photoacid generators, photobase generators, and photo radical polymerization initiators (photo radical generators) can be used.

[0233] (Photochromic compound) From the viewpoint of resolution, the thermoplastic resin layer preferably contains a photochromic compound. A photochromic compound is a compound having a function of fading by causing structural changes such as decomposition and isomerization upon light irradiation.

[0234] Examples of the photochromic compound include photo cationic polymerization initiators that may be contained in the photosensitive resin layer described above, and the preferred embodiments are the same except as described below.

[0235] From the viewpoints of sensitivity and resolution, the photochromic compound preferably contains at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and more preferably contains an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion. In addition, as the photochromic compound, a photochromic compound having the following structure is preferred.

[0236] [Chemical formula]

[0237] (Photo radical polymerization initiator) The thermoplastic resin layer may contain a photo radical polymerization initiator.

[0238] Examples of the photo radical polymerization initiator include photo radical polymerization initiators that may be contained in the photosensitive resin layer described above, and the preferred embodiments are the same.

[0239] (Photobase generator) The thermoplastic resin composition may contain a photobase generator.

[0240] The photo-base generator is not particularly limited as long as it is a known photo-base generator. For example, 2-nitrobenzyl cyclohexylcarbamate, triphenylmethanol, O-carbamoyl hydroxylamine, O-carbamoyl oxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III) tris(triphenylmethyl borate), 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 can be mentioned.

[0241] The compound C contained in the thermoplastic resin layer may be one kind or two or more kinds.

[0242] From the viewpoints of the visibility and resolution of the exposed part and the unexposed part, the content of the compound C is preferably 0.1% by mass to 10% by mass, and more preferably 0.5% by mass to 5% by mass with respect to the total mass of the thermoplastic resin layer.

[0243] (Plasticizer) From the viewpoints of resolution, adhesion to an adjacent layer, and developability, the thermoplastic resin layer preferably contains a plasticizer.

[0244] The plasticizer preferably has a smaller molecular weight (in the case of an oligomer or polymer having a molecular weight distribution, the weight average molecular weight) than the alkali-soluble resin. The molecular weight (weight average molecular weight) of the plasticizer is preferably 200 to 2,000.

[0245] The plasticizer is not particularly limited as long as it is a compound that is compatible with alkali-soluble resins and exhibits plasticity. However, from the viewpoint of imparting plasticity, the plasticizer preferably has an alkylene oxy group in its molecule, and polyalkylene glycol compounds are more preferred. The alkylene oxy group contained in the plasticizer is more preferably a polyethylene oxy structure or a polypropylene oxy structure.

[0246] Furthermore, from the viewpoint of resolution and storage stability, it is preferable that the plasticizer contains a (meth)acrylate compound. From the viewpoint of compatibility, resolution, and adhesion to adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound.

[0247] Examples of (meth)acrylate compounds used as plasticizers include the (meth)acrylate compounds described as polymerizable compounds included in the photosensitive resin composition mentioned above.

[0248] In transfer films, when a thermoplastic resin layer and a photosensitive resin layer are laminated in direct contact, it is preferable that both the thermoplastic resin layer and the negative-type photosensitive layer contain the same (meth)acrylate compound. This is because the inclusion of the same (meth)acrylate compound in both the thermoplastic resin layer and the photosensitive resin layer suppresses the diffusion of components between layers, thereby improving storage stability.

[0249] When a thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, it is preferable that the (meth)acrylate compound does not polymerize in the exposed area after exposure, from the viewpoint of adhesion between the thermoplastic resin layer and adjacent layers.

[0250] Furthermore, as a (meth)acrylate compound used as a plasticizer, a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule is preferred from the viewpoint of resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability.

[0251] Furthermore, as the (meth)acrylate compound used as a plasticizer, (meth)acrylate compounds having an acid group or urethane (meth)acrylate compounds are also preferred.

[0252] The plasticizer contained in the thermoplastic resin layer may be one type or two or more types.

[0253] From the viewpoint of resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability, the plasticizer content is preferably 1% to 70% by mass, more preferably 10% to 60% by mass, and even more preferably 20% to 50% by mass, relative to the total mass of the thermoplastic resin layer.

[0254] (Sensitizer) The thermoplastic resin layer may contain a sensitizer.

[0255] The sensitizer is not particularly limited and may include the photosensitive resin layer mentioned above.

[0256] The thermoplastic resin layer may contain one type of sensitizer or two or more types.

[0257] The sensitizer content can be appropriately selected depending on the purpose, but from the viewpoint of improving sensitivity to the light source and visibility of the exposed and unexposed areas, 0.01% to 5% by mass, and more preferably 0.05% to 1% by mass, is preferred based on the total mass of the thermoplastic resin layer.

[0258] (Additives, etc.) The thermoplastic resin layer may contain known additives such as surfactants, in addition to the above components, as needed.

[0259] Furthermore, the thermoplastic resin layer is described in paragraphs

[0189] to

[0193] of Japanese Patent Publication No. 2014-085643, and the contents described in this publication are incorporated herein by reference.

[0260] The thickness of the thermoplastic resin layer is not particularly limited, but from the perspective of adhesion to an adjacent layer, it is preferably 1 μm or more, more preferably 2 μm or more. The upper limit is not particularly limited, but from the perspectives 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.

[0261] <Protective film> The transfer film of the present disclosure may have a protective film on the surface opposite to the intermediate layer side of the photosensitive resin layer.

[0262] As the protective film, a resin film can be used. Examples of the resin film include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films. Among them, from the perspective of heat resistance and the like, the protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film, and even more preferably a polyethylene film.

[0263] The average thickness of the protective film is not particularly limited, and from the perspective of mechanical strength and the like, 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.

[0264] <Use> The transfer film of the present disclosure is preferably used for forming circuit wirings disposed on a support substrate such as a sheet, a metal substrate, a ceramic substrate, and glass in a manufacturing process film of a semiconductor package, a printed circuit board, a flexible printed wiring board, and an interposer rewiring layer.

[0265] <Method for manufacturing transfer film> The method for manufacturing the transfer film of this disclosure is not particularly limited, but it is preferable to include in this order: a step of forming a thermoplastic resin layer on one side of a temporary support by coating (hereinafter also referred to as the "thermoplastic resin layer formation step"), a step of forming the intermediate layer on the side of the thermoplastic resin layer opposite to the side in contact with the temporary support by coating (hereinafter also referred to as the "intermediate layer formation step"), and a step of forming the photosensitive resin layer on the side of the intermediate layer opposite to the side in contact with the thermoplastic resin layer by coating (hereinafter also referred to as the "photosensitive resin layer formation step"). Furthermore, the method for manufacturing the transfer film of this disclosure may include a step of providing a protective film on the surface of the photosensitive resin layer (hereinafter referred to as the protective film placement step). In this specification, "drying" means the removal of at least a portion of the solvent contained in the composition. Examples of drying methods include natural drying, heat drying, and vacuum drying. These methods can be applied individually or in combination.

[0266] (Thermoplastic resin layer formation process) A thermoplastic resin layer forming composition used in the thermoplastic resin layer forming process can be prepared by dissolving or dispersing the material to be contained in the thermoplastic resin layer in a solvent. Examples of solvents include the aforementioned water-soluble solvents, alkylene glycol ethers, alkylene glycol ether acetates, ketone solvents (such as methyl ethyl ketone), aromatic hydrocarbon solvents (such as toluene), aprotic polar solvents (such as N,N-dimethylformamide), ether solvents (such as diethyl ether), ester solvents (such as n-propyl acetate), amide solvents, and lactone solvents. Methods for applying thermoplastic resin layer-forming compositions include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (i.e., slit coating). The drying temperature can be 80°C to 130°C. Note that the drying temperature refers to the temperature of the environment in which the thermoplastic resin layer-forming composition is dried. The drying time can be between 20 and 600 seconds.

[0267] (Intermediate layer formation process) The intermediate layer forming composition used in the intermediate layer forming process can be prepared by dissolving or dispersing the materials to be contained in the intermediate layer (such as surfactants) in a solvent. Examples of solvents include water and the aforementioned water-soluble solvents. The application method, drying temperature, and drying time for the intermediate layer-forming composition are the same as those for the thermoplastic resin layer-forming process, and are therefore omitted from this description.

[0268] (Photosensitive resin layer formation process) The application method, drying temperature, and drying time for the photosensitive resin composition are the same as those for the thermoplastic resin layer formation process, and are therefore omitted from this description.

[0269] (Protective film placement process) The protective film placement step may include laminating a protective film onto the surface of the photosensitive resin layer. The protective film can be applied using a known laminator such as a vacuum laminator or an auto-cut laminator. Preferably, the laminator is equipped with a heat-sensitive roller, such as a rubber roller, and is capable of applying pressure and heating.

[0270] [Method for manufacturing resin patterns] The method for manufacturing a resin pattern according to the present disclosure preferably comprises, in this order: a step of laminating a transfer film and a substrate so that the photosensitive resin layer in the transfer film of the present disclosure is in contact with the substrate (hereinafter also referred to as the "lamination step"), a step of pattern exposure to the photosensitive resin layer (hereinafter also referred to as the "exposure step"), a step of heating the photosensitive resin layer after exposure (hereinafter also referred to as the "post-exposure baking step"), and a step of developing the photosensitive resin layer after heating to form a resin pattern (hereinafter also referred to as the "development step").

[0271] (Lamination process) In the lamination process, it is preferable to bring the surface of the transfer film with the photosensitive resin layer into contact with the substrate and press it down. If the substrate is a conductive substrate as described later, it is preferable to bring the photosensitive resin layer into contact with the conductive layer and press it down. If the transfer film has a protective film as described later, it is preferable to perform the lamination process after peeling off the protective film.

[0272] Examples of bonding methods include known transfer methods and lamination methods. In particular, it is preferable to place the transfer film on the circuit board and apply pressure and heat using a roll or the like.

[0273] The transfer film and substrate can be bonded together using a known laminator such as a vacuum laminator or an auto-cut laminator.

[0274] The lamination temperature is not particularly limited. The lamination temperature is preferably, for example, 80°C to 150°C, more preferably 90°C to 150°C, and even more preferably 100°C to 150°C. When using a laminator equipped with rubber rollers, the lamination temperature refers to the temperature of the rubber rollers.

[0275] The substrate is preferably a conductive substrate (wiring substrate) having a support substrate and a conductive layer disposed on the support substrate.

[0276] Examples of support substrates include resin substrates, glass substrates, and semiconductor substrates. Preferred embodiments of the support substrate are described, for example, in paragraph 0140 of International Publication No. 2018 / 155193, which are incorporated herein by reference. Furthermore, if the support substrate is a resin substrate, it is preferable that the resin substrate material is a substrate containing a cycloolefin polymer, polyethylene terephthalate, or polyimide. The average thickness of the support substrate is not particularly limited and can range from 5.0 μm to 200.0 μm.

[0277] The conductive layer is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, from the viewpoint of conductivity and fine wire formation. Furthermore, the support substrate may have only one conductive layer or two or more conductive layers. When two or more conductive layers are arranged, it is preferable that the conductive layers be made of different materials. Preferred embodiments of the conductive layer are described, for example, in paragraph 0141 of International Publication No. 2018 / 155193, which are incorporated herein by reference.

[0278] A conductive substrate having at least one of transparent electrodes and routing wiring is preferred. A conductive substrate with such a configuration can be suitably used as a substrate for a touch panel. Transparent electrodes can function suitably as electrodes for touch panels. Preferably, transparent electrodes are composed of metal oxide films such as ITO (indium tin oxide) and IZO (indium zinc oxide), metal meshes, and metal nanowires. Examples of metal wires include those made of silver and copper. Among these, silver conductive materials such as silver mesh and silver nanowires are preferred.

[0279] Metal is preferred as the material for routing the wiring. Examples of metals used for wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, manganese, and alloys composed of two or more of these metal elements. Copper, molybdenum, aluminum, or titanium are preferred materials for wiring, with copper being particularly preferred.

[0280] The substrate may be a substrate into which elements that connect semiconductor elements to each other are incorporated. Examples of elements that connect semiconductor elements to each other include elements on which wiring patterns for interconnecting semiconductor elements are formed on a silicon substrate.

[0281] The substrate may have a seed layer on its surface. Examples of materials constituting the seed layer include copper, chromium, lead, nickel, gold, silver, tin, and zinc. The average thickness of the seed layer is not particularly limited and can be 50 nm to 2 μm. There are no particular limitations on the method of forming the seed layer, and examples include coating a dispersion of metal nanoparticles and sintering the coating film, sputtering, and vapor deposition.

[0282] From the viewpoint of reducing transmission loss, the dielectric loss tangent of the substrate at 24 GHz is preferably 0.05 or less, and more preferably 0.03 or less.

[0283] (Exposure process) The exposure process involves pattern exposure of the photosensitive resin layer. "Pattern exposure" refers to a form of exposure that is applied in a patterned manner, resulting in a mixture of exposed and unexposed areas.

[0284] The positional relationship between the exposed and unexposed areas in pattern exposure is not particularly limited and can be adjusted as appropriate.

[0285] Exposure may be performed from the photosensitive resin layer side or from the circuit board side.

[0286] The exposure method may also be contact exposure, which involves bringing a mask (also called a "photomask") into contact with a photosensitive resin layer.

[0287] Furthermore, the exposure method may be proximity exposure, lens projection exposure, mirror projection exposure, or direct exposure using an exposure laser, in addition to contact exposure. In the case of lens projection exposure, an exposure machine with an appropriate numerical aperture (NA) of the lens can be used depending on the required resolution and depth of field. In the case of direct exposure, drawing may be performed directly on the photosensitive resin layer, or reduction projection exposure may be performed on the photosensitive layer via a lens.

[0288] Furthermore, exposure may be performed in the atmosphere, under reduced pressure, or under vacuum. During exposure, a liquid such as water may be interposed between the light source and the photosensitive resin layer.

[0289] In particular, from the viewpoint of further improving resolution, projection exposure is preferred, and lens projection exposure is more preferred.

[0290] The detailed arrangement and specific size of the pattern in pattern exposure are not particularly limited.

[0291] From the viewpoint of achieving high resolution, in pattern exposure, the pattern width is preferably 5 μm or less, and more preferably 2.5 μm or less. The lower limit of the pattern width is not particularly limited, and is, for example, 1.0 μm.

[0292] The light source for exposure is not particularly limited. Examples of light sources include those capable of irradiating light in a wavelength range that can harden the exposed area (e.g., 365 nm or 405 nm). Specific examples of light sources include various lasers; semiconductor light sources such as light-emitting diodes (LEDs); and discharge lamps such as ultra-high pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps.

[0293] The amount of exposure is not particularly limited. The exposure dose is 5 mJ / cm². 2 ~200 mJ / cm 2 Preferably, it is 10 mJ / cm 2 ~200 mJ / cm 2 It is preferable that it be so.

[0294] (Post-sensing bake process) In the post-exposure baking process, the exposed photosensitive resin layer is heated. The photosensitive resin composition disclosed herein has a ratio of 10% to 50% of the total number of double bonds in the solid content of the photosensitive resin composition that is based on acryloyl groups, which is higher than conventional compositions. When the exposed photosensitive resin layer is heated within the above range, the reaction distribution originating from standing waves becomes uniform, and undercutting and drooping of the resin pattern are suppressed. In other words, the uniformity of the shape of the resin pattern is improved.

[0295] The post-exposure baking process is preferably carried out under conditions of a heating temperature of 50°C to 90°C and a heating time of 20 to 80 seconds.

[0296] When the heating temperature is 50°C or higher, the effect of improving the shape of the resin pattern due to heating is more easily obtained. If the heating temperature is 90°C or lower, the thermosetting reaction can be suppressed. From the above perspective, a heating temperature of 50°C to 90°C is more preferable. If the heating time is 20 seconds or longer, the effect of improving the shape of the resin pattern due to heating is more likely to be obtained. If the heating time is 80 seconds or less, the thermosetting reaction can be suppressed. From the above perspective, a heating time of 30 to 60 seconds is more preferable.

[0297] The step height on the surface of the photosensitive resin layer after the post-exposure baking process is preferably 0.1 μm or less, and more preferably 0.05 μm or less. The lower limit of the step height is not particularly limited, and the step height may be 0 μm. The step height on the surface of the photosensitive resin layer is measured by the following method. The cross-section of the resin pattern was cut and measured using a scanning electron microscope (SEM).

[0298] (Development process) In the developing process, the heated photosensitive resin layer is developed to form a resin pattern.

[0299] The exposed photosensitive resin layer can be developed using a developing solution.

[0300] The developer is not particularly limited, and any known developer can be used. Examples of developing solutions include the developing solution described in Japanese Patent Publication No. 5-72724.

[0301] The developing solution is preferably an alkaline aqueous solution. Examples of alkaline compounds that may be contained in alkaline aqueous solutions include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0302] The pH of the alkaline aqueous solution is not particularly limited. The pH of the alkaline aqueous solution at 25°C is preferably, for example, 8 to 13, more preferably 9 to 12, and even more preferably 10 to 12.

[0303] The content of the alkaline compound in the alkaline aqueous solution is not particularly limited, but is preferably 0.1% to 5% by mass, and more preferably 0.1% to 3% by mass, relative to the total mass of the alkaline aqueous solution.

[0304] The temperature of the developing solution is not particularly limited. The developer solution temperature is preferably, for example, 20°C to 40°C.

[0305] Examples of development methods include paddle development, shower development, spray development, shower and spin development, and dip development.

[0306] As for the development method, the development method described in paragraph

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

[0307] After the developing process, a rinsing treatment may be performed to remove the developer solution. Water or similar substances can be used for the rinsing treatment.

[0308] After the developing process and / or rinsing process, a drying process may be performed to remove excess liquid.

[0309] (Temporary support removal process) The method for manufacturing the resin pattern of this disclosure preferably includes a step of peeling off the temporary support in the transfer film (hereinafter also referred to as the "temporary support peeling step"). The method for peeling off the temporary support is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs

[0161] to

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

[0310] The temporary support peeling step is preferably performed after the bonding step and before the developing step. The temporary support peeling step may also be performed after the bonding step and before the exposure step, or after the exposure step. From the viewpoint of suppressing radical polymerization inhibition by oxygen during exposure and preventing mask contamination, it is preferable that the temporary support peeling process be performed after the lamination process and the exposure process, and before the development process. From the viewpoint of improving the resolution of the resin pattern and suppressing defects in the resin pattern, it is preferable that the temporary support peeling process be performed after the bonding process and before the exposure process.

[0311] The method for manufacturing a resin pattern according to this disclosure may include a step of further exposing the formed resin pattern to light (hereinafter also referred to as the "post-exposure step") and / or a step of further heating the formed resin pattern (hereinafter also referred to as the "post-bake step").

[0312] If the process includes both a post-exposure step and a post-bake step, it is preferable to perform the post-exposure step first, followed by the post-bake step.

[0313] The exposure dose in the post-exposure process is preferably 100 mJ / cm 2 ~5000 mJ / cm 2 and more preferably 200 mJ / cm 2 ~3000 mJ / cm 2 .

[0314] The heating temperature in the post-bake process is preferably 80°C to 250°C, and more preferably 90°C to 160°C. The heating time in the post-bake process is preferably 1 minute to 180 minutes, and more preferably 10 minutes to 60 minutes.

[0315] [Method for manufacturing a conductive pattern] As a first embodiment, the method for manufacturing a conductive pattern of the present disclosure includes a step of forming a resin pattern on a substrate using the method for manufacturing a resin pattern of the present disclosure, a step of performing plating treatment (hereinafter also referred to as "plating step") on an area of the substrate where the resin pattern is not formed, and a step of removing the resin pattern (hereinafter also referred to as "pattern removal step") in this order.

[0316] The details of the step of forming a resin pattern on the substrate are as described above.

[0317] (Plating step) Examples of the plating treatment method include electrolytic plating and electroless plating. Among them, from the viewpoint of productivity, electrolytic plating is preferably used for plating.

[0318] The metal used for the plating treatment is not particularly limited, and known metals can be used. Examples of the metals that can be used include copper, chromium, lead, nickel, gold, silver, tin, zinc, alloys of these metals, etc. From the viewpoint of conductivity, copper or its alloy is preferable.

[0319] The average thickness of the plating layer formed by the plating treatment is not particularly limited and can be 0.1 μm to 20.0 μm.

[0320] (Pattern removal step) There are no particular limitations on the method for removing the resin pattern, but one method is removal by chemical treatment, and a method using a removal solution is preferred. Examples of removal solutions include those obtained by dissolving inorganic or organic alkaline components in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of inorganic alkaline components include sodium hydroxide and potassium hydroxide. Examples of organic alkali components include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0321] The temperature of the removal solution is preferably 30°C to 80°C, and more preferably 50°C to 80°C. A preferred method of removal involves immersing a laminate having the pattern to be removed in a removal solution that is being stirred and has a liquid temperature of 50°C to 80°C for 1 to 30 minutes. Alternatively, the pattern may be removed using a removal solution and known methods such as the spray method, shower method, or paddle method.

[0322] (Protective layer formation process) The method for manufacturing a conductive pattern according to this disclosure may include a step of forming a protective layer on the surface of the plating layer after forming the resin pattern and before the pattern removal step (hereinafter also referred to as the "protective layer formation step"). The material constituting the protective layer is preferably one that does not dissolve in the removal solution or etching solution used in the pattern removal process or seed layer removal process. Examples of materials constituting the protective layer include nickel, chromium, tin, zinc, magnesium, gold, silver, alloys thereof, and resins. Nickel or chromium are preferred as materials constituting the protective layer.

[0323] Methods for forming the protective layer include electroless plating and electroplating, with electroplating being preferred.

[0324] The average thickness of the protective layer is not particularly limited and can be between 0.3 μm and 3.0 μm.

[0325] (Seed layer removal process) If the substrate has a seed layer on its surface, the method for manufacturing a conductive pattern according to this disclosure may include a step of removing the seed layer (hereinafter also referred to as the "seed layer removal step"). The seed layer removal step is a step of removing the exposed seed layer to obtain conductive nanowires.

[0326] The method for removing the seed layer is not particularly limited and may be carried out by using a known etching solution. Examples of etching solutions include ferric chloride solution, cupric chloride solution, ammonia-alkali solution, sulfuric acid-hydrogen peroxide mixture, and phosphoric acid-hydrogen peroxide mixture.

[0327] In a second embodiment, the method for manufacturing a conductive pattern of the present disclosure preferably comprises, in this order, the steps of: forming a resin pattern on a conductive layer of a conductive substrate (a substrate having a conductive layer) using the method for manufacturing a resin pattern of the present disclosure; etching areas of the substrate where the resin pattern is not formed (hereinafter also referred to as the "etching step"); and removing the resin pattern (hereinafter also referred to as the "pattern removal step").

[0328] The details of the process for forming a resin pattern on the substrate are as described above. A preferred embodiment of the substrate having a conductive layer is as described above. Furthermore, the preferred embodiment of the pattern removal process in the second embodiment is the same as the preferred embodiment of the pattern removal process in the first embodiment.

[0329] (Etching process) Known etching methods can be used as etching procedures. Specifically, examples include the methods described in paragraphs

[0209] to

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

[0048] to

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

[0330] For wet etching, the etching solution used can be appropriately selected as either acidic or alkaline depending on the object being etched.

[0331] Examples of acidic etching solutions include acidic aqueous solutions containing at least one acidic compound, and acidic mixed aqueous solutions of an acidic compound and at least one selected from the group consisting of ferric chloride, ammonium fluoride, and potassium permanganate.

[0332] The acidic compound (a compound that dissolves in water and exhibits acidity) contained in the acidic aqueous solution is preferably at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid.

[0333] Examples of alkaline etching solutions include an alkaline aqueous solution containing at least one alkaline compound, and an alkaline aqueous mixture of an alkaline compound and a salt (e.g., potassium permanganate).

[0334] The alkaline compound (a compound that dissolves in water and exhibits alkalinity) contained in the alkaline aqueous solution is preferably at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide).

[0335] It is preferable that the etching solution does not dissolve the resist pattern.

[0336] The developing solution used in the development process may also serve as the etching solution used in the etching process. In this case, the development and etching processes may be performed simultaneously.

[0337] After the etching process, a rinsing process may be performed to remove the etching solution. Water or similar substances can be used for the rinsing process.

[0338] After the etching and / or rinsing process, a drying process may be performed to remove any excess liquid.

[0339] Furthermore, a circuit wiring board may be manufactured using the transfer film of this disclosure. A method for manufacturing a circuit wiring board may include a step of forming a solder resist layer having openings on the surface of a substrate from which the seed layer has been removed, using solder resist (hereinafter also referred to as the "solder resist layer formation step"). The opening is preferably designed to expose the conductive pattern formed on the surface of the substrate. Conventional known solder resists can be used. Examples of solder resists include azide-cyclized polyisoprene resins, azide-phenol resins, and chloromethyl polystyrene resins. The average thickness of the solder resist layer is not particularly limited and can be between 5 μm and 50 μm. The method for forming the solder resist layer is not particularly limited and can be carried out by conventionally known methods.

[0340] A method for manufacturing a circuit wiring board may include a step of forming bump electrodes in the openings of the solder resist layer. Preferably, the bump electrodes are connected to the conductor patterns exposed at the openings.

[0341] A method for manufacturing a circuit wiring board may include a step of mounting semiconductor elements that connect to bump electrodes. The semiconductor to be mounted preferably has electrodes, and it is preferable to connect these electrodes to the bump electrodes. After mounting the semiconductor, it is preferable to seal the semiconductor using a conventionally known sealing material.

[0342] <Semiconductor Packages> The semiconductor package preferably includes the circuit wiring substrate described above.

[0343] <Manufacturing method for printed circuit boards> The transfer film of this disclosure can be used in the manufacture of printed circuit boards. A method for manufacturing a printed circuit board includes, for example, a step of applying at least one treatment selected from the group consisting of etching and plating to a substrate having the pattern described above in the method for manufacturing a laminate. Here, the etching or plating of the substrate can be performed by etching or plating the surface of the substrate using a known method, with the developed pattern as a mask. Furthermore, prior to etching or plating, a process to remove residual film may be performed using resin etching with a chemical solution containing permanganate or resin ashing with plasma.

[0344] Examples of etching solutions that can be used include cupric chloride solution, ferric chloride solution, and alkaline etching solution. Examples of plating include copper plating, solder plating, nickel plating, and gold plating.

[0345] After etching or plating, the pattern can be removed using, for example, an aqueous solution that is even more strongly alkaline than the alkaline aqueous solution used for developing. Examples of such strongly alkaline aqueous solutions include 1% to 10% by mass sodium hydroxide aqueous solution and 1% to 10% by mass potassium hydroxide aqueous solution. Examples of removal methods include immersion and spraying. The printed circuit board on which the pattern is formed may be a multilayer printed circuit board and may have small-diameter through-holes.

[0346] When plating is performed on a substrate equipped with a conductive layer, it is necessary to remove the conductive layer other than the pattern. Methods for this removal include, for example, light etching after peeling off the pattern; or, after the above plating is performed, solder plating or the like is performed, then the pattern is peeled off to mask the wiring portion with solder, and then the conductive layer in the unmasked portion is treated with an etching solution that can etch only that portion.

[0347] <Vapor deposition mask> The transfer film of this disclosure can be used particularly suitably for microfabrication of metal substrates for vapor deposition masks having fine irregularities on their surface. The method for manufacturing a vapor deposition mask includes a step of etching a substrate having the pattern described above in the method for manufacturing a laminate. Here, the etching of the substrate can be performed by etching the surface of the substrate using a known method, with the developed pattern as a mask. After etching, the pattern can be removed using an aqueous solution that is even more strongly alkaline than the alkaline aqueous solution used for development. Examples of such strongly alkaline aqueous solutions include 1% to 10% by mass sodium hydroxide aqueous solutions and 1% to 10% by mass potassium hydroxide aqueous solutions. Examples of removal methods include immersion and spraying. [Examples]

[0348] The present disclosure will be further described in detail below with reference to examples. The materials, quantities, proportions, processing details, and processing procedures shown in the following examples may be modified as appropriate, provided that they do not deviate from the spirit of this disclosure. Therefore, the scope of this disclosure is not limited to the specific examples shown below.

[0349] <Preparation of photosensitive resin composition> The components used in the preparation of the photosensitive resin composition are as follows:

[0350] (Alkali-soluble resin) Alkali-soluble resins A1 to A4 were synthesized using known methods. The weight-average molecular weight (Mw) of the synthesized polymers was measured by gel permeation chromatography (GPC) under the following conditions.

[0351] -GPC conditions- Equipment: Tosoh Corporation, Tosoh High-Speed ​​GPC System HLC-8420GPC (product name) Guard column: Tosoh Corporation, HZ-L Separation column: A column consisting of three TSK gel Super HZM-N (product name) columns manufactured by Tosoh Corporation, connected in series. Measurement temperature: 40℃ Eluent: THF (tetrahydrofuran) Flow rate: Sample pump 0.35 mL / min, Reference pump 0.175 mL / min Injection volume: 10μL Detector: Differential refractometer GPC column calibration standard solution: Standard polystyrene manufactured by Tosoh Corporation

[0352] -Alkali-soluble resin A1- 67 g of propylene glycol monomethyl ether was placed in a flask and heated to 90°C under a nitrogen stream. To this solution, 63.7 g of styrene, 1.3 g of methyl methacrylate, 35 g of methacrylic acid, and 4 g of polymerization initiator V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were dissolved in 33 g of propylene glycol monomethyl ether and added dropwise over 3 hours. After the dropwise addition was complete, 1 g of V-601 was added three times at 1-hour intervals. The reaction was then allowed to proceed for another 3 hours. After the reaction, the reaction solution was diluted with 33 g of propylene glycol monomethyl ether acetate and 100 g of propylene glycol monomethyl ether. Under an air stream, the diluted reaction solution was heated to 100°C, and 0.53 g of tetraethylammonium bromide and 0.26 g of p-methoxyphenol were added. 32 g of glycidyl methacrylate (Bremmer G, manufactured by NOF Corporation) was added dropwise to this solution over 20 minutes. After reacting this solution 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%. Alkali-soluble resin A1: St / MAA / MMA / MAA-GMA = 63.7 / 19 / 1.3 / 16 (mass ratio), weight-average molecular weight 18,000

[0353] -Alkali-soluble resins A2, A3- Alkali-soluble resins A2 and A3 were synthesized using the same method as for alkali-soluble resin A1. Alkali-soluble resin A2:St / MAA / MMA / MAA-GMA=47.7 / 19 / 1.3. / 32 (mass ratio), weight average molecular weight 18,000 Alkali-soluble resin A3: St / MAA / MMA / MAA-GMA = 31.7 / 19 / 1.3 / 48 (mass ratio), weight-average molecular weight 18,000

[0354] St: Styrene (manufactured by Fujifilm Wako Pure Chemical Corporation) MAA: Methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Corporation) MMA: Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Corporation) MAA-GMA: A structure in which glycidyl methacrylate is added to a structural unit derived from methacrylic acid.

[0355] -Alkali-soluble resin A4- A solution containing monomer M1, methacrylic acid, methyl methacrylate, styrene, polymerization initiator V-601, and N-methylpyrrolidone (21.5 g) was added dropwise over 2 hours to N-methylpyrrolidone (21.5 g) heated to 90°C under a nitrogen stream. After the addition of the solution was complete, 0.5 g of V-601 was added dropwise three times at 1-hour intervals. The mixture was reacted at 90°C for 3 hours and then cooled to room temperature. The reaction solution was diluted with N-methylpyrrolidone, triethylamine and 4-methoxyphenol were added, and the mixture was stirred 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 collected 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 forced-air dryer at 50 degrees Celsius and diluted with propylene glycol monomethyl ether acetate to obtain a solution of alkali-soluble resin A4 with a solid content of 30%.

[0356] [ka]

[0357] The structure of alkali-soluble resin A4 is as follows. The numerical values ​​for each structural unit represent the mass ratio. The weight-average molecular weight of alkali-soluble resin A4 was 18,000. [ka]

[0358] (Multifunctional (meth)acrylate) BPE-100: 2,2-bis(4-(methacryloylethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. BPE-500: 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. ABE-300: 2,2-bis(4-(acryloylethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. A-DCP: Tricyclodecanedimethanol diacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. • Aronics M-270: Polypropylene glycol diacrylate (n≒12), manufactured by Toagosei Co., Ltd., listed as "M-270" in the table.

[0359] (Polymerization initiator) • B-CIM: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, manufactured by Hampford.

[0360] (Sensitizer) SB-PI 701: 4,4'-bis(diethylamino)benzophenone, manufactured by Sanyo Trading Co., Ltd.

[0361] (Chain transfer agent) N-phenylcarbamoylmethyl-N-carboxymethylaniline: Manufactured by Fujifilm Wako Pure Chemical Corporation

[0362] (dye) • Leucocrystal violet: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0363] (Rust inhibitor) • CBT-1: Carboxybenzotriazole, manufactured by Johoku Chemical Co., Ltd.

[0364] (Polymerization inhibitor) • TDP-G: Phenothiazine, manufactured by Kawaguchi Chemical Co., Ltd.

[0365] (Surfactants) • Polymer W1: A polymer synthesized by the following method.

[0366] A 300 mL three-necked flask equipped with a condenser, thermometer, stirring blade, and nitrogen inlet tube was heated to 80°C with 14.0 g of cyclopentanone. A mixed solution of 18.00 g (42.6 mmol) of Cyraprene™-0701T (JNC), 12.00 g (30.2 mmol) of compound (a) below, 0.25 g (1.1 mmol) of V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.), and 56.00 g of cyclopentanone was added dropwise over 120 minutes. After aging for 1 hour, a mixed solution of 0.17 g (0.7 mmol) of V-601 and 1.40 g of cyclopentanone was added, and the mixture was aged for another 1 hour. Furthermore, a mixed solution of 0.17 g (0.7 mmol) of V-601 and 1.40 g of cyclopentanone was added, and the mixture was aged for 3 hours to obtain 98.5 g of the target polymer W1 solution. The weight-average molecular weight (Mw) of the obtained W1 was 24700, and the Mw / Mn ratio was 2.8. The reaction progress was also confirmed by NMR.

[0367] [ka]

[0368] The structure of polymer W1 is as follows. The numerical values ​​for each structural unit indicate the mass ratio.

[0369] [ka]

[0370] (solvent) • MMPG-Ac: 1-Methoxy-2-propylacetate • MEK: Methyl ethyl ketone • PGME: Propylene glycol monomethyl ether

[0371] Each component was mixed according to the information in Table 1 to prepare photosensitive resin compositions P1-P6 and P1a-P3a. The values ​​in the table represent the content of each component in parts by mass.

[0372] [Table 1]

[0373] <Preparation of composition for forming the intermediate layer> The components used in the preparation of the intermediate layer-forming composition are as follows:

[0374] (resin) • PVA: Polyvinyl alcohol, product name "Kuraray Poval PVA-205", manufactured by Kuraray Co., Ltd. • PVP: Polyvinylpyrrolidone, product name "Polyvinylpyrrolidone K-30", manufactured by Nippon Shokubai Co., Ltd. • HPMC: Hydroxypropyl methylcellulose, product name "Metrolose 60SH-03", manufactured by Shin-Etsu Chemical Co., Ltd.

[0375] (Surfactants) • Silicone-based surfactant, product name "BYK-345", manufactured by BIC Chemie Japan Co., Ltd.

[0376] (solvent) ·Pure water • MeOH: methanol

[0377] The components were mixed according to the information in Table 2 to prepare the intermediate layer forming composition M1. The values ​​in the table represent the content of each component in parts by mass.

[0378] [Table 2]

[0379] <Preparation of composition for forming thermoplastic resin layer> The components used in the preparation of the thermoplastic resin layer forming composition are as follows:

[0380] (resin) • 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

[0381] (Plasticizer) A-DCP: Tricyclodecanedimethanol diacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. • 8UX-015A: Urethane acrylate (manufactured by Taisei Fine Chemical Co., Ltd.) • Arronix TO-2349: Polyfunctional acrylate containing carboxyl groups (manufactured by Toagosei Co., Ltd.)

[0382] (Rust inhibitor) • CBT-1: Carboxybenzotriazole, manufactured by Johoku Chemical Co., Ltd.

[0383] (Polymerization inhibitor) • TDP-G: Phenothiazine, manufactured by Kawaguchi Chemical Co., Ltd.

[0384] (Photoacid generator) Compound 1: Represented by the following structure.

[0385] [ka]

[0386] Compound 2: Represented by the following structure.

[0387] [ka]

[0388] (Surfactants) • Polymer W1

[0389] (solvent) • MMPG-Ac: 1-Methoxy-2-propylacetate • MEK: Methyl ethyl ketone • PGME: Propylene glycol monomethyl ether

[0390] Compositions T1 to T3 for forming thermoplastic resin layers were prepared by mixing each component according to the information in Table 3. The values ​​in the table represent the content of each component in parts by mass.

[0391] [Table 3]

[0392] <Manufacturing of transfer film> Table 4 shows the types of photosensitive resin compositions used to form the photosensitive resin layer, the types of thermoplastic resin layer-forming compositions used to form the thermoplastic resin, and the types of intermediate layer-forming compositions used to form the intermediate layer.

[0393] A thermoplastic resin layer-forming composition was applied to a temporary support (polyethylene terephthalate film, thickness: 16 μm, haze: 0.12%) using a slit nozzle, with a coating width of 1.0 m and a dry layer thickness of 6.0 μm. The formed coating was dried at 80°C for 40 seconds to form a thermoplastic resin layer. An intermediate layer-forming composition was applied to the formed thermoplastic resin layer using a slit nozzle, with a coating width of 1.0 m and a dry layer thickness of 1.2 μm. The coating was dried at 80°C for 40 seconds to form an intermediate layer. A photosensitive resin composition was applied to the formed intermediate layer using a slit nozzle, with a coating width of 1.0 m and a dry layer thickness of 3.0 μm, and dried in a 100°C convection oven for 2 minutes to form a photosensitive resin layer. A transfer film was prepared by laminating a protective film (polypropylene film, thickness: 12 μm, haze: 0.2%) onto a photosensitive resin layer.

[0394] The following evaluations were performed using the prepared transfer film.

[0395] <Resolution> A silicon wafer with a seed layer formed on it was prepared as the substrate. The fabricated transfer film was laminated onto the substrate (lamination process). The lamination was performed using a 100°C heat roll at a pressure of 0.7 MPa and a speed of 2 m / min. Next, the temporary support was removed (temporary support removal process). Pattern exposure was performed using a projection exposure system with a theoretical resolution of 1.5 μm and a high-pressure mercury lamp as the light source, via a mask (exposure process). The exposure amount was determined by using a 41-step step tablet manufactured by Stouffer, and developing the sample for 2.0 times the minimum development time, resulting in 13 remaining step levels. The minimum development time refers to the time it takes for the photosensitive resin layer to completely disappear when developing from an unexposed state. As a mask, a mask was used that included a wiring pattern (L = 1 μm to 2 μm, in 0.1 μm increments, 10 lines) such that the line (L) / space (S) ratio in the resin pattern was 1 / 1. After exposure, the photosensitive resin layer was heated at the heating temperature and heating time shown in Table 5 (post-exposure baking step). In Example 8, the post-exposure baking step was not performed. After exposure, the material was developed for twice the minimum development time to obtain a resin pattern. The "resolution" value was defined as the pattern L / S that showed no residue or peeling.

[0396] <Shape> The resin patterns obtained from the resolution evaluation described above were cut perpendicular to the substrate. The cross-sections of the resin patterns were observed using a scanning electron microscope (SEM: S-4800 (Hitachi High-Tech)). Perpendicular lines were drawn from two corners at the top (outermost layer) of the resin pattern towards the bottom of the resin pattern. The distance between the corners at the bottom of the resin pattern and the perpendicular lines was measured, and the average value was calculated. Furthermore, if the bottom corner of the resin pattern is outside the perpendicular line, it is called a "hem-dragging" pattern. An undercut is defined as a resin pattern where the bottom corner lies inside a perpendicular line. A: The average distance is 0.05 μm or less. B: The average distance is greater than 0.05 μm and less than or equal to 0.1 μm. C: The average distance is greater than 0.1 μm and less than or equal to 0.15 μm. D: The average distance is greater than 0.15 μm.

[0397] Table 5 shows the evaluation results. In Table 5, the "Total Double Bond Content," "Double Bond Content Based on Acryloyl Groups," "Double Bond Content Based on Methacryloyl Groups," and "Double Bond Content of Alkali-Soluble Resins" are based on the total amount of solids in the photosensitive resin composition. "The proportion of double bonds based on acryloyl groups" refers to the proportion of double bonds based on acryloyl groups to the total number of double bonds in the solid content of the photosensitive resin composition. "The proportion of double bonds in alkali-soluble resin" refers to the proportion of double bonds in alkali-soluble resin to the total number of double bonds in the solid content of the photosensitive resin composition. "Polymerization inhibitor / acryloyl group-based double bond" refers to the molar ratio of the polymerization inhibitor content to the acryloyl group-based double bond content.

[0398] [Table 4]

[0399] As shown in Table 4, in Examples 1 to 12, the photosensitive resin composition contained an alkali-soluble resin containing a crosslinkable group having a double bond, a polyfunctional (meth)acrylate, and a polymerization inhibitor. The total double bond content in the solids of the photosensitive resin composition was 2.00 mmol / g or more relative to the total amount of solids of the photosensitive resin composition, the proportion of double bonds based on acryloyl groups to the total number of double bonds in the solids of the photosensitive resin composition was 10% to 50%, and the molar ratio of the polymerization inhibitor content to the content of double bonds based on acryloyl groups was 0.001 to 0.015. As a result, it was possible to form a resin pattern with a good shape and excellent resolution.

[0400] On the other hand, in Comparative Example 1, the proportion of double bonds based on acryloyl groups was less than 10%, resulting in a poorly shaped resin pattern. In Comparative Example 2, the proportion of double bonds based on acryloyl groups exceeded 50%, resulting in a poorly shaped resin pattern. In Comparative Example 3, the total double bond content in the solid content of the photosensitive resin composition was less than 2.00 mmol / g, resulting in a poorly shaped resin pattern and inferior resolution.

[0401] In Example 2, the proportion of double bonds in the alkali-soluble resin was 20% or more, and it was found that the shape of the resin pattern was better compared to Example 1. In Example 3, the proportion of double bonds in the alkali-soluble resin was 40% or less, and it was found that the shape of the resin pattern was better compared to Example 4.

[0402] Furthermore, the step height on the surface of the photosensitive resin layer was measured using the transfer film of Example 12. Similar to the resolution evaluation method described above, the bonding process, temporary support peeling process, exposure process, and post-exposure baking process were performed. The obtained photosensitive resin layer had a shape with a 2 μm unevenness pitch, where the cross-section of the transparent areas was convex and the cross-section of the light-blocking areas was concave in L / S = 2 μm / 2 μm pattern exposure. The step height on the surface of the photosensitive resin layer was 0.03 μm. [Explanation of Symbols]

[0403] 11: Temporary support 12: Transfer layer 17: Photosensitive resin layer 13: Thermoplastic resin layer 15: Middle Class 19: Protective film 20: Transfer film

Claims

1. A photosensitive resin composition comprising an alkali-soluble resin containing a crosslinkable group having a double bond, a polyfunctional (meth)acrylate, and a polymerization inhibitor. The total double bond content in the solid content of the photosensitive resin composition is 2.00 mmol / g or more relative to the total amount of solid content of the photosensitive resin composition. The proportion of double bonds based on acryloyl groups to the total number of double bonds in the solid content of the photosensitive resin composition is 10% to 50%. A photosensitive resin composition in which the molar ratio of the content of the polymerization inhibitor to the content of double bonds based on acryloyl groups is 0.001 to 0.

015.

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

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

4. The photosensitive resin composition according to claim 1, wherein the polyfunctional (meth)acrylate comprises a bifunctional (meth)acrylate.

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

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

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

8. The transfer film according to claim 7, wherein the thermoplastic resin layer contains a photobleaching compound.

9. A step of bonding the transfer film and the substrate such that the photosensitive resin layer in the transfer film according to claim 5 is in contact with the substrate, A step of pattern exposure to the photosensitive resin layer after lamination, A step of heating the photosensitive resin layer after exposure, A method for manufacturing a resin pattern, comprising the steps of developing a photosensitive resin layer after heating to form a resin pattern, in this order.

10. The method for manufacturing a resin pattern according to claim 9, wherein the step of heating the photosensitive resin layer after exposure is performed under the conditions of a heating temperature of 50°C to 90°C and a heating time of 20 seconds to 80 seconds.

11. The method for manufacturing a resin pattern according to claim 9, further comprising the step of peeling off the temporary support after the step of bonding the transfer film and the substrate, and before the step of exposure of the pattern.

12. A method for producing a resin pattern according to claim 9, wherein the step height on the surface of the photosensitive resin layer after heating is 0.1 μm or less.

13. A step of forming the resin pattern on a substrate using the resin pattern manufacturing method described in claim 9, A step of performing a plating treatment on the region of the substrate where the resin pattern is not formed, A step of removing the aforementioned resin pattern, A method for manufacturing a conductive pattern having the following elements in this order.

14. A step of forming the resin pattern on a conductive substrate using the resin pattern manufacturing method described in claim 9, A step of etching the region of the conductive substrate where the resin pattern is not formed, A step of removing the aforementioned resin pattern, A method for manufacturing a conductive pattern having the following elements in this order.

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