Method for forming resist pattern, and photosensitive resin laminate

Abstract

Provided is a method for forming a resist pattern that includes a circular hole portion having an aspect ratio of 2.5 or greater, the method comprising: (1) a step for laminating, on a base material, a photosensitive resin laminate that includes a support film and a photosensitive resin layer having a film thickness of 100 μm or greater; (2) a step for exposing the photosensitive resin layer after lamination; and (3) a step for developing and removing unexposed portions of the photosensitive resin layer after exposure.　The photosensitive resin layer contains an alkali-soluble polymer containing an aromatic-ring-including monomer as a copolymerization component. In the minimum development time of the photosensitive resin layer consisting only of unexposed portions, the development speed of the photosensitive resin layer is 0.25-3.00 μm / s. The development time in the step (3) is at least 2.5 times the minimum development time of the photosensitive resin layer consisting only of unexposed portions.

Description

Method for forming a resist pattern and photosensitive resin laminate

[0001] The present disclosure relates to a method for forming a resist pattern and a photosensitive resin laminate.

[0002] Conventionally, the manufacture of printed wiring boards, precision machining of metals, etc. have been manufactured by photolithography methods. The photosensitive resin laminates used in photolithography methods are classified into negative types that dissolve and remove unexposed portions and positive types that dissolve and remove exposed portions.

[0003] A general method for forming a pattern using a photosensitive resin laminate will be briefly described. First, the protective layer is peeled off from the photosensitive resin laminate. Using a laminator, the photosensitive resin layer and the support are laminated on a substrate such as a copper-clad laminate or a copper sputtered thin film in the order of the substrate, the photosensitive resin layer, and the support. The photosensitive resin layer is exposed through a photomask having a desired wiring pattern. The support is peeled off from the exposed laminate, and a resist pattern is formed on the substrate by dissolving or dispersing and removing the unexposed portion or the exposed portion with a developer. After subjecting the substrate provided with the resist pattern to plating treatments such as copper plating and solder plating, the resist pattern is peeled off, whereby a metal pattern can be formed, wiring, metal pillars or semiconductor bumps can be formed, and semiconductor mounting can be performed.

[0004] Various photosensitive resin laminates have been studied for forming a resist pattern or a metal pattern using the same. For example, Patent Documents 1 to 3 describe photosensitive resin laminates having a photosensitive resin layer containing a specific alkali-soluble polymer, a photopolymerizable monomer, and a photopolymerization initiator. Further, Patent Document 2 also studies the relationship between the film thickness and absorbance of the photosensitive resin layer.

[0005] International Publication No. 2011 / 037182 International Publication No. 2021 / 095784 International Publication No. 2022 / 085366

[0006] In recent years, there has been a demand for miniaturization and increased density of wiring, and consequently, plating methods have expanded as a method for forming metal wiring. The shape of the wiring formed by the plating method depends on the shape and thickness of the resist pattern. In the plating method, a photosensitive resin laminate having a thick photosensitive resin layer is generally used, and the resist pattern formed by exposure and development of the photosensitive resin laminate is subjected to metal plating and then treated with a stripping solution.

[0007] Photosensitive resins used in plating processes require a reduction in the phenomenon where the plating penetrates the bottom of the cured resist pattern during the plating process (hereinafter also referred to as "plating penetration") and the resulting phenomenon of the metal pattern being pulled back.

[0008] Problems with the peelability of cured resist patterns or plating penetration are particularly pronounced in the formation of metal cylinders or polygonal prism patterns using thick photosensitive resin layers or perforated resist patterns, such as resist patterns with a specified ratio of film thickness to hole diameter (aspect ratio: film thickness / hole diameter), peeling with dimethyl sulfoxide (DMSO)-free peeling solutions to reduce environmental impact, and wafer-level packaging (WLP).

[0009] In particular, to achieve even higher density, metal pillars with higher aspect ratios are required, and a pattern formation method is needed that can form circular hole patterns with higher aspect ratios with higher resolution.

[0010] Therefore, the present disclosure aims to provide a method for forming a resist pattern that can form a circular hole pattern with a higher aspect ratio, and a photosensitive resin laminate.

[0011] The inventors have found that the above problems can be solved by optimizing the combination of exposure conditions and development conditions for the photosensitive resin layer, and have completed the present invention. Examples of embodiments of this disclosure are listed in the following sections. [1] A method for forming a resist pattern including a circular hole portion with an aspect ratio of 2.5 or more, comprising: (1) a step of laminating a photosensitive resin laminate including a support film and a photosensitive resin layer having a thickness of 100 μm or more onto a substrate; (2) a step of exposing the laminated photosensitive resin layer; and (3) a step of developing and removing the unexposed portion of the photosensitive resin layer after exposure, wherein the photosensitive resin layer contains an alkali-soluble polymer containing a monomer having an aromatic ring as a copolymer component, the development speed of the photosensitive resin layer is 0.25 μm / s or more and 3.00 μm / s or less at the minimum development time of the photosensitive resin layer consisting only of the unexposed portion, and the development time in step (3) is 2.5 times or more the minimum development time of the photosensitive resin layer consisting only of the unexposed portion. [2] The method for forming a resist pattern according to [1], wherein the ratio A / T of the absorbance (A) at 365 nm to the film thickness (T) [μm] of the photosensitive resin layer is 0.003 or less. [3] The method for forming a resist pattern according to [1] or [2], wherein the amount of sensitizer contained in the photosensitive resin layer is 0.005% by mass or less based on the total mass of the photosensitive resin layer. [4] In step (3), Na as the developer ２ CO ３A method for forming a resist pattern according to any one of [1] to [3], using an aqueous solution. [5] A method for forming a resist pattern according to any one of [1] to [4], wherein in step (2), exposure is performed using a projection exposure machine equipped with a lens having a numerical aperture (NA) of 0.16 or less. [6] A method for forming a resist pattern according to any one of [1] to [4], wherein in step (2), exposure is performed using a projection exposure machine equipped with a lens having a numerical aperture (NA) of 0.10 or less. [7] A method for forming a resist pattern according to any one of [1] to [6], wherein the formed resist pattern includes a circular hole portion having an aspect ratio of 3.0 or more. [8] The photosensitive resin layer is exposed in step (2) using a projection exposure machine equipped with a lens having a numerical aperture (NA) of 0.16 or less, and in step (3), 1% by mass of Na as a developer. ２ CO ３ A method for forming a resist pattern according to any one of [1] to [7], wherein, when an aqueous solution is used and the development time is set to 2.5 times the minimum development time for a photosensitive resin layer consisting only of unexposed areas, a resist pattern including a circular hole portion with an aspect ratio of 3.0 or more can be formed by steps (1) to (3). [9] The photosensitive resin layer is exposed in step (2) using a projection exposure machine equipped with a lens having an numerical aperture (NA) of 0.16 or less, and in step (3) a developer solution containing 1% by mass of Na ２ CO ３A method for forming a resist pattern according to any one of [1] to [7], wherein, when an aqueous solution is used and the development time is set to 3.0 times the minimum development time for a photosensitive resin layer consisting only of unexposed areas, a resist pattern including circular hole portions with an aspect ratio of 4 or more can be formed by steps (1) to (3).

[10] A method for forming a resist pattern according to any one of [1] to [9], comprising, after steps (1) to (3), (6) a step of metal plating on circular hole portions on a substrate with an aspect ratio of 3.0 or more; and (7) a step of peeling off the portion of the photosensitive resin layer exposed in step (2); to form a metal pillar pattern with an aspect ratio of 2.7 or more.

[11] A method for forming a resist pattern according to any one of [1] to [9], wherein a photosensitive resin laminate is laminated onto a copper substrate, exposed using a projection exposure machine equipped with a lens having a numerical aperture (NA) of 0.16 or less, and 1% by mass of Na is used as the developer. ２ CO ３ A photosensitive resin laminate used to form a circular hole with an aspect ratio of 3.0 or more by developing it with an aqueous solution for a development time of 2.5 times or more the minimum development time, characterized in that the photosensitive resin layer in the photosensitive resin laminate has a film thickness of 100 μm or more, and further contains an alkali-soluble polymer component containing a monomer having an aromatic ring as a copolymer component.

[12] The photosensitive resin laminate according to

[11] , wherein the development speed of the photosensitive resin layer is 0.25 μm / s or more and 3.00 μm / s or less.

[13] The photosensitive resin laminate according to

[11] or

[12] , wherein the ratio A / T of the absorbance (A) at 365 nm to the film thickness (T) [μm] of the photosensitive resin layer is 0.003 or less.

[0012] This disclosure provides a method for forming a resist pattern that can form a circular hole pattern with a higher aspect ratio, and a photosensitive resin laminate, which in turn can improve developability and resolution, and can form a resist pattern that includes circular hole portions with an aspect ratio of 2.5 or higher.

[0013] "Photosensitive Resin Laminate" The photosensitive resin laminate of the present disclosure includes a support film and a photosensitive resin layer laminated on the support film. The photosensitive resin laminate is preferably a dry film resist. The photosensitive resin layer may have a protective layer on the surface opposite to the support film side if necessary.

[0014] The photosensitive resin laminate of the present disclosure is characterized in that the photosensitive resin layer has a film thickness of 100 μm or more and contains an alkali-soluble polymer component containing a monomer having an aromatic ring as a copolymerization component.

[0015] Then, the photosensitive resin laminate of the present disclosure is laminated on a copper substrate, exposed using a projection exposure machine equipped with a lens having a numerical aperture (NA) of 0.16 or less, and 1% by mass of Na ２ CO ３ An aqueous solution is used for development at a development time of 2.5 times or more the minimum development time to form circular holes having an aspect ratio of 3.0 or more. <UNK>

[0016] In particular, in the photosensitive resin laminate of the present disclosure, the film thickness of the photosensitive resin layer being 100 μm or more makes it suitable for forming circular holes with a high aspect ratio. Also, the alkali-soluble polymer containing a copolymer having a monomer having an aromatic ring as a copolymerization component results in excellent resolution of the resist pattern.

[0017] By using the photosensitive resin laminate of the present disclosure having the above-described configuration and optimizing the combination of the exposure conditions and development conditions of the photosensitive resin layer in the resist pattern forming method of the present disclosure described later, a resist pattern including circular hole portions having an aspect ratio of 2.5 or more, preferably 3.0 or more, more preferably 4.0 or more, and still more preferably 6.0 or more can be preferably formed.

[0018] The common configurations, preferred embodiments, etc. in the present disclosure will be described below.

[0019] <(A) Alkali-soluble polymer> The photosensitive resin composition and the photosensitive resin layer contain an alkali-soluble polymer. The amount of alkali-soluble polymer is 30% to 70% by mass, preferably 40% to 70% by mass, and more preferably 50% to 70% by mass, based on the total solid content mass of the photosensitive resin composition or the photosensitive resin layer. In this specification, an alkali-soluble polymer is a polymer that can be dissolved in an alkaline aqueous solution.

[0020] Alkali-soluble polymers include copolymers in which monomers having aromatic rings are copolymerized components. Alkali-soluble polymers containing monomers having aromatic rings as copolymerized components are hydrophobic and have a swelling-suppressing effect, resulting in excellent resolution of resist patterns. From the viewpoint of swelling-suppressing effect and resolution, the mass ratio of units having aromatic rings in the alkali-soluble polymer is preferably in the range of 50 to 90% by mass, more preferably 70 to 90% by mass, and even more preferably 75 to 85% by mass.

[0021] Examples of monomers having an aromatic ring include (meth)acrylates having an aromatic group, and aromatic vinyl compounds such as styrene and styrene derivatives. In this specification, (meth)acrylate means acrylate or methacrylate, (meth)acrylic means acrylic or methacrylic, and (meth)acryloyl means acryloyl or methacryloyl. Examples of styrene derivatives include oxystyrene, hydroxystyrene, acetoxystyrene, alkylstyrene, and halogenoalkylstyrene. Among these, (meth)acrylates having an aromatic group are preferred from the viewpoint of the developability of the resist pattern.

[0022] The aromatic group of the (meth)acrylate having an aromatic group is preferably an aromatic group having 6 to 20 carbon atoms, such as a phenyl group, benzyl group, biphenyl group, and naphthyl group. The hydrogen atoms of the aromatic group may be unsubstituted or substituted, and if substituted, examples of substituents include hydrocarbon groups having 1 to 5 carbon atoms, hydroxyl groups, halogen groups, etc.

[0023] Alkali-soluble polymers preferably contain a copolymer with benzyl (meth)acrylate as the copolymer component, as the (meth)acrylate having an aromatic group. Generally, aromatic rings are hydrophobic and therefore are expected to have low developability, but benzyl (meth)acrylate is highly flexible and has excellent developability, so alkali-soluble polymers preferably contain benzyl (meth)acrylate as the copolymer component.

[0024] The ratio of benzyl (meth)acrylate included as a copolymer component in the alkali-soluble polymer may be 40% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the total mass of monomers constituting the alkali-soluble polymer. A higher ratio of benzyl (meth)acrylate included as a copolymer component in the alkali-soluble polymer makes it easier to shorten the tail length of the resist pattern. The amount of benzyl (meth)acrylate is preferably less than 100% by mass, more preferably 95% by mass or less, and even more preferably 90% by mass or less, based on the total amount of monomers constituting the alkali-soluble polymer.

[0025] The alkali-soluble polymer has an acid equivalent of 350 or more, preferably 370 or more, more preferably 380 or more, even more preferably 390 or more, even more preferably 400 or more, and particularly preferably 410 or more. Here, acid equivalent refers to the weight of the alkali-soluble polymer per 1 mol of acidic groups, and the unit is g / mol. The acid equivalent can be calculated from the acid value (mgKOH / g) obtained from the weight of potassium hydroxide that reacts with 1 g of alkali-soluble polymer. That is, the acid equivalent can be measured by potentiometric titration using an aqueous potassium hydroxide solution (JIS K2501 (2003)), etc. An acid equivalent of 350 or more offers advantages such as shortening the minimum development time, improving resolution, reducing stripping solution fatigue, preventing resist wrinkles during storage, and shortening the bottom length of the resist pattern. There is no upper limit to the acid equivalent, but for example, it is preferably 600 or less. An acid equivalent of 600 or less can improve developability and stripping properties.

[0026] The lower the ratio of acid groups in the alkali-soluble polymer, the more effectively swelling can be suppressed, and the better the resolution tends to be. Therefore, the ratio of acid groups is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, based on the solid content mass of the alkali-soluble polymer. The lower limit of the ratio of acid groups in the alkali-soluble polymer is not particularly limited, but for example, it may be 0% by mass, may exceed 0% by mass, or may be 1% by mass or more.

[0027] The lower the weight-average molecular weight of the alkali-soluble polymer, the better the developability and detachment dissolution tend to be. Therefore, the upper limit of the weight-average molecular weight of the alkali-soluble polymer may be 60,000 or less, preferably less than 60,000, more preferably 50,000 or less, even more preferably 40,000 or less, and particularly preferably 30,000 or less. The lower limit of the weight-average molecular weight of the alkali-soluble polymer is preferably 5,000 or more, more preferably 6,000 or more, from the viewpoint of reducing developed aggregates and improving the properties of the unexposed film in the photosensitive resin laminate, such as edge fusing and cut-tip properties. Edge fusing refers to the property of suppressing the phenomenon of the photosensitive resin layer protruding from the end face of the roll when the photosensitive resin laminate is wound into a roll. Cut-tip properties refer to the property of suppressing the phenomenon of chips flying off when the unexposed film is cut with a cutter. If the chip cutting performance is poor, scattered chips may adhere to surfaces such as the top surface of a photosensitive resin laminate, and these chips may be transferred to the mask during the subsequent exposure process, potentially causing defects.

[0028] The alkali-soluble polymer may contain copolymer components other than monomers having aromatic rings. Examples of such copolymer components include carboxylic acids, carboxylates, and acid anhydrides having at least one polymerizable unsaturated group in the molecule, such as (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid semi-ester (meth)acrylic acid, alkyl (meth)acrylate; (meth)acrylonitrile, (meth)acrylamide, etc. Among these, it is preferable that the copolymer component contains a constituent unit derived from (meth)acrylic acid. The total amount of methacrylic acid and acrylic acid in the alkali-soluble polymer is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, based on the solid content mass of the alkali-soluble polymer.

[0029] Alkali-soluble polymers are preferable if they contain constituent units derived from methacrylic acid, as this allows for a balance between excellent developability and resolution. When methacrylic acid is contained in an alkali-soluble polymer, the upper limit of its ratio is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, based on the solid content mass of the alkali-soluble polymer. The lower limit of the mass ratio of constituent units derived from methacrylic acid in the alkali-soluble polymer is not limited, but may be, for example, 0% by mass or greater than 0% by mass.

[0030] Alkali-soluble polymers are preferable if they contain constituent units derived from acrylic acid, as this results in excellent flexibility of the cured film and cured resist pattern, and consequently, excellent developability. From the viewpoint of flexibility and developability, the upper limit of the mass ratio of constituent units derived from acrylic acid in the alkali-soluble polymer is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, based on the solid content mass of the alkali-soluble polymer. The lower limit of the mass ratio of constituent units derived from acrylic acid in the alkali-soluble polymer is not limited, but may be, for example, 0% by mass, may exceed 0% by mass, or may be 1% by mass or more.

[0031] Alkali-soluble polymers are preferable if they contain alkyl group-containing monomers (e.g., alkyl (meth)acrylates) because this results in excellent flexibility of the cured film and cured resist pattern, and consequently, excellent developability. From the viewpoint of flexibility and developability, the mass ratio of constituent units derived from alkyl group-containing monomers in the alkali-soluble polymer may be 1 to 40% by mass, preferably 1 to 20% by mass, and more preferably 1 to 10% by mass, based on the solid content mass of the alkali-soluble polymer.

[0032] Since alkali-soluble polymers tend to exhibit better flexibility and developability the longer their alkyl chains are, alkali-soluble polymers preferably contain alkyl groups having 1 to 10 carbon atoms, more preferably 4 to 10 carbon atoms, and even more preferably 6 to 10 carbon atoms.

[0033] The alkyl group of the alkyl (meth)acrylate may be linear, branched, or cyclic, and the number of carbon atoms may be, for example, 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, 12 or less, 11 or less, 10 or less, 9 or less, or 8 or less. More specifically, examples of alkyl groups of the alkyl (meth)acrylate include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, ethylhexyl group (e.g., 2-ethylhexyl group), nonyl group, decyl group, undecyl group, and dodecyl group. Among these, the 2-ethylhexyl group is even more preferred from the viewpoint of shortening the development time and reducing the trailing of the resist pattern. By using, for example, 2-ethylhexyl (meth)acrylate as part of the monomer used in the synthesis of alkali-soluble polymers, an alkali-soluble polymer containing 2-ethylhexyl acrylate as a copolymer component can be obtained.

[0034] Preferred combinations of copolymer components in alkali-soluble polymers include, for example, (meth)acrylic acid and benzyl (meth)acrylate; (meth)acrylic acid and benzyl (meth)acrylate and aromatic vinyl compounds; and (meth)acrylic acid and benzyl (meth)acrylate and alkyl (meth)acrylate. More specifically, examples include methacrylic acid and benzyl methacrylate; methacrylic acid and benzyl methacrylate and styrene; methacrylic acid and benzyl methacrylate and methyl methacrylate; and methacrylic acid and benzyl methacrylate and 2-ethylhexyl acrylate.

[0035] <(B) Compounds having ethylenically unsaturated bonds> The photosensitive resin composition and photosensitive resin layer according to this embodiment contain compounds having ethylenically unsaturated bonds. The amount of compound having ethylenically unsaturated bonds is 20% to 50% by mass, preferably 20% to 40% by mass, based on the total solid content mass of the photosensitive resin composition or photosensitive resin layer. The ethylenically unsaturated bonds can be polymerized by irradiation with light in the presence of a photopolymerization initiator, thereby curing the photosensitive resin layer.

[0036] Compounds having ethylenically unsaturated bonds may have a lower limit of double bond equivalent of 150 or more, preferably 160 or more, more preferably 170 or more, even more preferably 180 or more, even more preferably 190 or more, and particularly preferably 200 or more. When the double bond equivalent of a compound having ethylenically unsaturated bonds is 150 or more, the resistance to plating penetration and peeling tend to improve. The upper limit of the double bond equivalent of a compound having ethylenically unsaturated bonds is not limited, but may be, for example, 500 or less, 400 or less, or 300 or less. In this specification, "double bond equivalent" means the molecular weight per ethylenically unsaturated bond.

[0037] From the viewpoint of improving resolution, the lower limit of the concentration of ethylenically unsaturated bonds in the photosensitive resin layer is preferably 1.0 mmol / g or more, more preferably 1.5 mmol / g or more, and even more preferably 2.0 mmol / g or more. When the concentration of ethylenically unsaturated bonds in the photosensitive resin layer is 1.0 mmol / g or more, a strong crosslinked film is formed as a resist pattern, which has a swelling suppression effect and tends to have excellent resolution. The ethylenically unsaturated bonds in the photosensitive resin layer are preferably derived from at least ethylenically unsaturated methacryloyl groups or acryloyl groups. The upper limit of the concentration of ethylenically unsaturated bonds in the photosensitive resin layer is not limited, but may be, for example, 5.0 mmol / g or less, 3.0 mmol / g or less, or 2.0 mmol / g or less. In this specification, "concentration of ethylenically unsaturated bonds in the photosensitive resin layer" means the total number of moles of ethylenically unsaturated bonding groups per gram of the photosensitive resin layer.

[0038] As a compound having an ethylenically unsaturated bond, for example, a compound having a (meth)acryloyl group can be used. In this disclosure, we do not wish to be bound by theory, but the dissolution mechanism of a photosensitive resin laminate or resist pattern in a stripping solution such as an aqueous solution of tetraalkylammonium hydroxide is thought to be that the compound having an ethylenically unsaturated bond contained in the photosensitive resin layer is hydrolyzed, and the crosslinked portion of the photosensitive resin layer dissolves in the stripping solution while decomposing. Based on the above dissolution mechanism, a compound having an acryloyl group (acrylate monomer) is preferred over a compound having a methacryloyl group (methacrylate monomer) because it has better hydrolytic properties and the acrylate monomer is easily dissolved and stripped in the stripping process.

[0039] Similar to the dissolution mechanism described above, from the viewpoint of solubility of the resist pattern in the stripping solution, the mass ratio (methacrylate monomer / acrylate monomer) of the compound having a methacryloyl group to the compound having an acryloyl group in the compound having an ethylenically unsaturated bond is preferably 0 or more and less than 0.5, and more preferably 0 or more and less than 0.1. Since acrylate monomers are more hydrolyzable than methacrylate monomers and tend to decompose more easily in the stripping solution, it is preferable that the compound having an ethylenically unsaturated bond contains a larger amount of acrylate monomer than methacrylate monomer. Furthermore, it is preferable that the methacrylate monomer is not contained in the compound having an ethylenically unsaturated bond, or is contained in a mass ratio of less than half that of the acrylate monomer.

[0040] Similar to the dissolution mechanism described above, the ratio of methacrylate monomer in the compound having an ethylenically unsaturated bond is preferably less than 50% by mass, more preferably less than 30% by mass, even more preferably less than 20% by mass, even more preferably less than 10% by mass, still even more preferably less than 5% by mass, particularly preferably less than 3% by mass, and most preferably 0% by mass, based on the mass of the compound having an ethylenically unsaturated bond, from the viewpoint of solubility in the stripping solution and hydrolysis.

[0041] Compounds having an ethylenically unsaturated bond can, if desired, be modified with alkylene oxides, specifically, they can have one or more alkylene oxide chains in their molecule. Examples of alkylene oxides include methylene oxide (MO), ethylene oxide (EO), propylene oxide (PO), trimethylene oxide, butylene oxide (BO), and tetramethylene oxide.

[0042] These alkylene oxides are often ethylene oxide (EO), which has two carbon atoms, or alkylene oxides with three or more carbon atoms. Among alkylene oxides with three or more carbon atoms, propylene oxide (PO) or butylene oxide (BO) are particularly often used. The number of carbon atoms in alkylene oxides with three or more carbon atoms may be, for example, six or less, five or less, or four or less.

[0043] When a compound having an ethylenically unsaturated bond has a relatively hydrophilic side chain, it tends to have good solubility in stripping solutions containing a large amount of water or hydrophilic solvent. Therefore, the alkylene oxide chain of the above compound is preferably relatively hydrophilic, and more preferably an ethylene oxide (EO) chain. As a compound having an ethylenically unsaturated bond with a relatively hydrophilic side chain, i.e., an alkylene oxide-modified compound (monomer) having an ethylenically unsaturated bond, monomers modified with alkylene oxide having 3 or more carbon atoms are preferred, and monomers modified with EO are more preferred. Therefore, the mass ratio of monomers modified with alkylene oxide having 3 or more carbon atoms to EO-modified monomers ((monomers modified with alkylene oxide having 3 or more carbon atoms) / EO-modified monomer) is preferably 0 or more and less than 0.1 from the viewpoint of solubility in stripping solutions. In this disclosure, monomers that do not have an alkylene oxide chain are calculated as EO-modified monomers.

[0044] When a compound having an ethylenically unsaturated bond has a relatively hydrophilic side chain, it tends to have good solubility in stripping solutions containing a large amount of water or hydrophilic solvent. Therefore, EO-modified monomers are preferred over relatively hydrophobic PO-modified and BO-modified monomers. Furthermore, the mass ratio of PO and / or BO-modified monomers to EO-modified monomers in a compound having an ethylenically unsaturated bond ((PO-modified monomer and / or BO-modified monomer) / EO-modified monomer) is preferably 0 or more and less than 0.1 from the viewpoint of solubility in stripping solutions. Monomers without alkylene oxide chains are calculated as EO-modified monomers. From a similar viewpoint, the mass ratio of PO monomer and / or BO monomer to EO-modified monomer in a compound having an ethylenically unsaturated bond ((PO-modified monomer and / or BO-modified monomer) / EO-modified monomer) is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, particularly preferably 5% by mass or less, and most preferably 0% by mass, based on the total solid content mass of the compound having an ethylenically unsaturated bond.

[0045] Regarding the EO chain length of compounds having ethylenically unsaturated bonds, shorter chains tend to result in better resolution, while longer chains tend to result in better developability. The number of moles of EO units in compounds having ethylenically unsaturated bonds is preferably in the range of 1 to 30, more preferably 4 to 20, and even more preferably 4 to 10 per mole of compound, from the viewpoint of balancing resolution and developability. Note that if the number of moles of EO units exceeds 1, the compound having ethylenically unsaturated bonds includes repeating units having EO chains.

[0046] The number of functional groups in a compound having ethylenically unsaturated bonds tends to be better in terms of resolution when there are more, and better in terms of exfoliation when there are fewer, so it can be determined according to the balance between resolution and exfoliation. The number of functional groups in a compound having ethylenically unsaturated bonds may be, for example, monofunctional (hereinafter also called monofunctional), two or more functional, three or more functional, four or more functional, five or more functional, six or more functional, three to ten functional, three to six functional, or four to six functional, or multiple types of compounds with different numbers of functional groups may be combined. In this specification, "number of functional groups" refers to the number of ethylenically unsaturated bonds per molecule of the compound, and for example, in the case of acrylate monomers, it is defined as the number of acryloyl groups per molecule, and in the case of methacrylate monomers, it is defined as the number of methacryloyl groups per molecule.

[0047] Compounds having a monofunctional ethylenically double bond are preferred because they have excellent solubility in the stripping solution. Examples of compounds having a monofunctional ethylenically double bond include compounds in which (meth)acrylic acid is added to one end of (poly)alkylene glycol, and compounds in which (meth)acrylic acid is added to one end of (poly)alkylene glycol and a group without an ethylenically double bond, such as an alkyl group, is added to the other end. The alkylene in (poly)alkylene glycol is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, such as a 1,2-ethylene group, a 1,2-propylene group, or a butylene group. From the viewpoint of solubility in the stripping solution, the content ratio of monofunctional monomers in the compound having an ethylenically double bond is preferably in the range of 1 to 30% by mass, more preferably 1 to 20% by mass, and even more preferably 5 to 15% by mass, based on the total solid content mass of the compound having an ethylenically unsaturated bond.

[0048] Examples of compounds with two or more functionalities include compounds having a backbone such as (poly)alkylene glycol, bisphenol A, trimethylolpropane, glycerin, pentaerythritol, or dipentaerythritol, in which at least two or all of the hydrogen atoms of the hydroxyl groups are substituted with functional groups having ethylenically unsaturated bonds, preferably functional groups having (meth)acryloyl groups, and more preferably functional groups having acryloyl groups.

[0049] A compound having a (poly)alkylene glycol backbone and a bifunctional ethylenically unsaturated bond is given by the following general formula (I): {In the formula, Y independently represents an alkylene group, and R １ and R ２ Each of the terms represents either a methyl group or a hydrogen atom, and each of the terms represents an integer from 1 to 50. Examples of compounds represented by} are shown.

[0050] In the above general formula (I), Y is independently preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, such as a 1,2-ethylene group, a 1,2-propylene group, and a butylene group. The (Y-O) portion may contain repeating units of different alkylene oxides, or it may consist of repeating units of the same alkylene oxide. When the (Y-O) portion contains different alkylene oxides, its arrangement may be random, alternating, or block arrangement. n represents an integer from 1 to 50, preferably 3 to 20, more preferably 6 to 10.

[0051] More specifically, examples of compounds represented by the above general formula (I) include: hexaethylene glycol diacrylate, heptaethylene glycol diacrylate, octaethylene glycol diacrylate, nonaethylene glycol diacrylate, decaethylene glycol diacrylate, hexapropylene glycol diacrylate, heptapropylene glycol diacrylate, octapropylene glycol diacrylate, nonapropylene glycol diacrylate, and decapropylene glycol diacrylate.

[0052] The double bond equivalent of the (meth)acrylate monomer represented by the above general formula (I) is preferably 150 or more, more preferably 160 or more, even more preferably 170 or more, and even more preferably 180 or more, and arbitrarily 500 or less, 400 or less, or 300 or less, from the viewpoint of resistance to plating penetration, treatment with stripping solution, and fatigue resistance with stripping solution.

[0053] In one example of this embodiment, the difunctional monomer is preferably a compound having a cyclic group, an ethylene oxide (EO) chain, and two acryloyl groups in one molecule (B-1). When a photosensitive resin composition or photosensitive resin layer contains the (B-1) compound, it tends to have excellent developability, resolution, and solubility in stripping solutions. Furthermore, the presence of a cyclic group in the (B-1) compound tends to improve resistance to plating penetration. In the (B-1) compound, there may be one or more cyclic groups, the EO chain may be located on one or both sides of the cyclic group, and the two acryloyl groups may be in any position.

[0054] (B-1) The EO chain of compound (B-1) is preferably located on both sides of the cyclic group, as a higher proportion of it improves solubility in stripping solutions containing a large amount of water or hydrophilic solvent. The number of moles of the EO chain of compound (B-1) is preferably in the range of 1 to 30, more preferably 4 to 20, and even more preferably 4 to 10, from the viewpoint of balancing resolution and developability.

[0055] (B-1) An example of a compound is a compound having hydrogenated bisphenol A as its skeleton, in which both sides of the hydrogenated bisphenol A skeleton are modified with EO, and which has acryloyl groups at both ends. Hydrogenated bisphenol A is a compound in which hydrogen is added to the aromatic ring of bisphenol A.

[0056] (B-1) Compounds in which the cyclic group is an aromatic ring are preferred. That is, (B-) compounds are preferred to have an aromatic ring, an ethylene oxide (EO) chain, and two acryloyl groups in one molecule. The presence of an aromatic ring as the cyclic group tends to improve resistance to plating penetration. Examples of such compounds include those with a bisphenol A skeleton, in which both sides of the bisphenol A skeleton are EO-modified and have acryloyl groups at both ends. The bisphenol A skeleton in (B-1) compounds not only improves the strength of the crosslinked film but also improves resolution.

[0057] A compound having a bisphenol A skeleton, in which both sides of the bisphenol A skeleton are modified with ethylene oxide (EO), and having acryloyl groups at both ends, is preferably a diacrylate of ethylene oxide (EO)-modified bisphenol A. The following general formula (II) is used for diacrylates of ethylene oxide-modified bisphenol A: Examples of compounds represented by the formula {wherein EO each independently represents ethylene oxide, A each independently represents an acryloyl group, and m and n each independently represent an integer from 1 to 100} are given. In general formula (II), from the viewpoint of improving the peelability of the resist pattern, m and n preferably satisfy the relationship 5 ≤ m + n ≤ 20, more preferably 7 ≤ m + n ≤ 15, even more preferably 8 ≤ m + n ≤ 12, and particularly preferably m + n ≈ 10.

[0058] More specifically, as compounds represented by the above general formula (II), for example: Diacrylate of polyethylene glycol obtained by adding an average of 1 mole of ethylene oxide to each end of bisphenol A, Diacrylate of polyethylene glycol obtained by adding an average of 2 moles of ethylene oxide to each end of bisphenol A, Diacrylate of polyethylene glycol obtained by adding an average of 3 moles of ethylene oxide to each end of bisphenol A, Diacrylate of polyethylene glycol obtained by adding an average of 4 moles of ethylene oxide to each end of bisphenol A, Diacrylate of polyethylene glycol obtained by adding an average of 5 moles of ethylene oxide to each end of bisphenol A, Diacrylate of polyethylene glycol obtained by adding an average of 6 to 9 moles of ethylene oxide to each end of bisphenol A, Diacrylate of polyethylene glycol obtained by adding an average of 10 moles of ethylene oxide to each end of bisphenol A, Diacrylate of polyethylene glycol obtained by adding an average of 11 to 19 moles of ethylene oxide to each end of bisphenol A, Examples include polyethylene glycol diacrylates obtained by adding an average of 20 moles of ethylene oxide to each end of bisphenol A, polyethylene glycol diacrylates obtained by adding an average of 21 to 29 moles of ethylene oxide to each end of bisphenol A, polyethylene glycol diacrylates obtained by adding an average of 30 moles of ethylene oxide to each end of bisphenol A, and polyethylene glycol diacrylates obtained by adding an average of 31 moles or more of ethylene oxide to each end of bisphenol A.

[0059] The double bond equivalent of the compound represented by the above general formula (II) is preferably 150 or more, more preferably 160 or more, even more preferably 170 or more, and even more preferably 180 or more, and arbitrarily 500 or less, 400 or less, or 300 or less, from the viewpoint of resistance to plating penetration, treatment with stripping solution, and fatigue resistance with stripping solution.

[0060] In one example of this embodiment, the photosensitive resin composition or photosensitive resin layer preferably contains a polyfunctional monomer with three or more functions as a compound having an ethylenically unsaturated bond.

[0061] In another example of this embodiment, at least two monomers are preferred as the compound having an ethylenically unsaturated bond, and a combination of a difunctional monomer and a trifunctional or polyfunctional monomer is more preferred.

[0062] As a polyfunctional monomer with three or more functions, a compound having three or more (B-2) acryloyl groups is preferred. When a photosensitive resin composition or photosensitive resin layer contains a (B-2) compound, it tends to have excellent developability, resolution, and solubility in stripping solutions. As a (B-2) compound, for example, among the polyfunctional monomers with three or more functions described later, those having an acryloyl group as a group having an ethylenically unsaturated bond may be used.

[0063] A compound with a trimethylolpropane backbone and a trifunctional ethylenically unsaturated bond is given by the following general formula (III): {In the formula, n １ , n ２ and n ３ Each of these is an integer between 1 and 25, where n is independent. １ +n ２ +n ３ R is an integer between 3 and 75. １ , R ２ and R ３ Each of these is independently either a methyl group or a hydrogen atom. Examples of compounds represented by} include:

[0064] In the above general formula (III), n １ , n ２ and n ３ Each of these is an integer between 1 and 25, preferably between 1 and 10, and more preferably between 1 and 3. １ +n ２ +n ３ n is an integer between 3 and 75, preferably 3 and 30, more preferably 3 and 15, and even more preferably 3 and 9. １ +n ２ +n ３ A value of 9 or higher is preferable from the viewpoint of suppressing the formation of resist trimmings, improving film strength, and imparting flexibility to the cured film. １ +n ２ +n ３A value of 75 or less is preferable from the viewpoint of high resolution and adhesion, good peeling characteristics, and control of edge fusing properties.

[0065] Specific examples of compounds represented by the above general formula (III) include, for example: triacrylates obtained by adding a total of an average of 3 moles of ethylene oxide to the hydroxyl groups of trimethylolpropane; triacrylates obtained by adding a total of an average of 9 moles of ethylene oxide to the hydroxyl groups of trimethylolpropane; triacrylates obtained by adding a total of an average of 15 moles of ethylene oxide to the hydroxyl groups of trimethylolpropane; and triacrylates obtained by adding a total of an average of 30 moles of ethylene oxide to the hydroxyl groups of trimethylolpropane.

[0066] The double bond equivalent of the (meth)acrylate monomer represented by the above general formula (III) is preferably 150 or more, more preferably 160 or more, even more preferably 170 or more, and even more preferably 180 or more, and arbitrarily 500 or less, 400 or less, or 300 or less, from the viewpoint of resistance to plating penetration, treatment with stripping solution, and fatigue resistance with stripping solution.

[0067] A compound with a glycerol backbone and a trifunctional ethylenically unsaturated bond is given by the following general formula (IV): Examples of compounds represented by the formula {wherein Y independently represents an alkylene group, R independently represents a methyl group or a hydrogen atom, and n independently represents an integer from 0 to 200} include:

[0068] In general formula (IV), Y is independently preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, such as a 1,2-ethylene group, a 1,2-propylene group, and a butylene group. From the viewpoint of imparting flexibility to the cured film, improving film strength, suppressing development aggregation, and enhancing the reactivity of ethylenically unsaturated bonds, it is preferable that at least one or all of Y are 1,2-ethylene groups. The (Y-O) portion may contain repeating units of different alkylene oxides, or it may consist of repeating units of the same alkylene oxide. When the (Y-O) portion contains different alkylene oxides, its arrangement may be random, alternating, or block arrangement. Each n is independently an integer from 0 to 200, preferably at least one n is an integer from 1 to 200, and more preferably three n are integers from 1 to 200. In general formula (IV), n may be 0, meaning that the alkylene oxide portion may not be present. A total of n of 1 or more is preferable from the viewpoint of suppressing the formation of resist edges, improving film strength, and imparting flexibility to the cured film. A total of n of 200 or less is preferable from the viewpoint of high resolution and adhesion, good peelability, and control of edge fusing properties.

[0069] The double bond equivalent of the (meth)acrylate monomer represented by the above general formula (IV) is preferably 150 or more, more preferably 160 or more, even more preferably 170 or more, and even more preferably 180 or more, and arbitrarily 500 or less, 400 or less, or 300 or less, from the viewpoint of resistance to plating penetration, treatment with stripping solution, and fatigue resistance with stripping solution.

[0070] A compound with a pentaerythritol backbone and four functional ethylenically unsaturated bonds is given by the following general formula (V): {In the formula, n １ , n ２ , n ３ and n ４ Each of these independently represents an integer from 1 to 25, and n １ +n ２ +n ３ +n ４ is an integer between 4 and 100, and R１ , R ２ , R ３ and R ４ Each of these independently represents a methyl group or a hydrogen atom, R ５ , R ６ , R ７ , and R ８ Each of these independently represents an alkylene group, R ５ , R ６ , R ７ and R ８ If there are multiple instances of each, then the multiple R ５ , R ６ , R ７ and R ８ Compounds represented by} may be identical or different from each other.

[0071] In general formula (V), R ５ , R ６ , R ７ and R ８ Each of these is independently preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, for example, a 1,2-ethylene group, a 1,2-propylene group, and a butylene group. From the viewpoint of imparting flexibility to the cured film, improving film strength, suppressing development aggregation, and enhancing the reactivity of ethylenically unsaturated bonds, R ５ , R ６ , R ７ and R ８ Preferably, at least one or all of them are 1,2-ethylene groups. １ +n ２ +n ３ +n ４ n is 4 to 100, preferably 4 to 80, more preferably 4 to 40, even more preferably 4 to 20, and particularly preferably 4 to 16. １ +n ２ +n ３ +n ４ A value of 4 or higher is preferable from the viewpoint of suppressing the formation of resist trimmings, improving film strength, and imparting flexibility to the cured film. １ +n ２ +n ３ +n ４A value of 100 or less is preferable from the viewpoint of high resolution and adhesion, good peeling characteristics, and control of edge fusing properties.

[0072] Specific examples of compounds represented by the above general formula (V) include, for example: tetraacrylate obtained by adding a total of an average of 4 moles of ethylene oxide to the terminals of the hydroxyl groups of pentaerythritol; tetraacrylate obtained by adding a total of an average of 9 moles of ethylene oxide to the terminals of the hydroxyl groups of pentaerythritol; tetraacrylate obtained by adding a total of an average of 12 moles of ethylene oxide to the terminals of the hydroxyl groups of pentaerythritol; tetraacrylate obtained by adding a total of an average of 15 moles of ethylene oxide to the terminals of the hydroxyl groups of pentaerythritol; tetraacrylate obtained by adding a total of an average of 20 moles of ethylene oxide to the terminals of the hydroxyl groups of pentaerythritol; tetraacrylate obtained by adding a total of an average of 28 moles of ethylene oxide to the terminals of the hydroxyl groups of pentaerythritol; and tetraacrylate obtained by adding a total of an average of 35 moles of ethylene oxide to the terminals of the hydroxyl groups of pentaerythritol.

[0073] The double bond equivalent of the (meth)acrylate monomer represented by the above general formula (V) is preferably 150 or more, more preferably 160 or more, even more preferably 170 or more, and even more preferably 180 or more, and arbitrarily 500 or less, 400 or less, or 300 or less, from the viewpoint of resistance to plating penetration, treatment with stripping solution, and fatigue resistance with stripping solution.

[0074] Among compounds with a pentaerythritol backbone and four functional ethylenically unsaturated bonds, the (B-2) compound is the following general formula (V1): Compounds represented by the formula {wherein EO each independently represents ethylene oxide, A each independently represents an acryloyl group, and k, l, m, and n each independently represent an integer from 1 to 100} are preferred. Compounds represented by the general formula (V1) can improve crosslinking density and, consequently, contribute to good resolution. In the general formula (V1), k, l, m, and n preferably satisfy the relationship 4 ≤ k + l + m + n ≤ 100, more preferably 10 ≤ k + l + m + n ≤ 50, even more preferably 12 ≤ k + l + m + n ≤ 25, and particularly preferably k + l + m + n ≈ 15 from the viewpoint of improving the peelability of the resist pattern.

[0075] A compound with a dipentaerythritol backbone and six functional ethylenically unsaturated bonds is given by the following general formula (VI): Examples of compounds represented by the formula {wherein R independently represents a methyl group or a hydrogen atom, and n independently represents an integer from 0 to 30} include compounds represented by the formula (VI). In general formula (VI), n may be 0, that is, the alkylene oxide moiety may not be present.

[0076] In general formula (VI), n is an integer from 0 to 30, preferably 1 to 20, more preferably 2 to 10, and even more preferably 3 to 5. The sum of n is from 0 to 180, preferably 6 to 120, more preferably 12 to 60, and even more preferably 18 to 30. A sum of n of 1 or more is preferable from the viewpoint of suppressing the formation of resist edges, improving film strength, and imparting flexibility to the cured film. A sum of n of 180 or less is preferable from the viewpoint of high resolution and adhesion, good peelability, and control of edge fusing properties.

[0077] Specific examples of hexaacrylate compounds represented by general formula (VI) include, for example: dipentaerythritol hexaacrylate, hexaacrylate in which a total of 1 to 36 moles of ethylene oxide are added to the six ends of dipentaerythritol, hexaacrylate in which a total of 6 to 30 moles of ethylene oxide are added to the six ends of dipentaerythritol, hexaacrylate in which a total of 12 to 30 moles of ethylene oxide are added to the six ends of dipentaerythritol, hexaacrylate in which a total of 18 to 30 moles of ethylene oxide are added to the six ends of dipentaerythritol, and hexaacrylate in which a total of 1 to 10 moles of ε-caprolactone are added to the six ends of dipentaerythritol.

[0078] The double bond equivalent of the (meth)acrylate monomer represented by the above general formula (VI) is preferably 150 or more, more preferably 160 or more, even more preferably 170 or more, and even more preferably 180 or more, and arbitrarily 500 or less, 400 or less, or 300 or less, from the viewpoint of resistance to plating penetration, stripping solution treatment, and stripping solution fatigue.

[0079] The mass ratio (A / B) of the alkali-soluble polymer to the compound having an ethylenically unsaturated bond tends to improve the curability of the bottom of the resist film, resulting in superior stripping fluid fatigue resistance and resolution, while a lower mass ratio tends to improve developability. From the viewpoint of balancing resolution and developability, the mass ratio (A / B) is preferably in the range of 1.2 to 3.0, more preferably 1.5 to 2.5, even more preferably 1.7 to 2.5, even more preferably 1.8 to 2.3, and particularly preferably 1.8 to 2.2.

[0080] <(C) Photopolymerization initiator> A photopolymerization initiator is a compound that, when irradiated with light in the presence of a compound having an ethylenically unsaturated bond, can initiate the polymerization of the compound having the ethylenically unsaturated bond.

[0081] The amount of photopolymerization initiator in the photosensitive resin composition and the photosensitive resin layer is 0.01% to 20% by mass, preferably 0.3% to 10% by mass, and more preferably 1% to 5% by mass, based on the total solid content mass of the photosensitive resin composition and the photosensitive resin layer, respectively. If the amount of photopolymerization initiator is 0.01% by mass or more, an exposure pattern with a sufficient residual film rate can be obtained after development. If the amount of photopolymerization initiator is 20% by mass or less, light can be sufficiently transmitted to the bottom surface of the resist, high resolution can be obtained, and development aggregation in the developer can be suppressed.

[0082] Examples of photopolymerization initiators include imidazole compounds, aromatic ketones, acridine compounds, and N-aryl-α-amino acid compounds. A single photopolymerization initiator may be used, or two or more may be used in combination.

[0083] Imidazole compounds tend to suppress the resistance of resist patterns to plating penetration and trimming. Examples of imidazole compounds include imidazoles having aliphatic groups, such as methylimidazole, 2-ethyl-4-methylimidazole, 1-isobutyl-2-methylimidazole, 2-ethyl-4-methylimidazole, ethylimidazole, isopropylimidazole, 2,4-dimethylimidazole, undecylimidazole, heptadecylimidazole, etc., and imidazoles having aromatic groups, such as 1-benzyl-2-methylimidazole, phenylimidazole (2-phenylimidazole, etc.), 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, triarylimidazole, and their dimers. In particular, from the viewpoint of resistance to plating and suppression of plating penetration, imidazoles having aromatic groups are preferred, triarylimidazoles (e.g., rofin) or their dimers are more preferred, and triarylimidazole dimers are even more preferred.

[0084] Examples of triarylimidazole dimers include 2,4,5-triarylimidazole dimers such as 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. Among these, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred.

[0085] Aromatic ketones are preferred from the viewpoint of improving sensitivity. Examples of aromatic ketones include benzophenone, 2-benzyl-2-dimethylamino-1-(4-monofornophenyl)butanone-1, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1.

[0086] Acridine compounds are preferred from the viewpoint of improving sensitivity and achieving both high sensitivity and suppression of stabilization. Examples of acridine compounds include 1,7-bis(9,9'-acridinyl)heptane, 9-phenylacridine, 9-methylacridine, 9-ethylacridine, 9-chloroethylacridine, 9-methoxyacridine, 9-ethoxyacridine, 9-(4-methylphenyl)acridine, 9-(4-ethylphenyl)acridine, 9-(4-n-propylphenyl)acridine, 9-(4-n-butylphenyl)acridine, 9-(4-tert-butylphenyl)acridine, 9-(4-methoxyphenyl)acridine, 9-(4-ethoxyphenyl)acridine, and 9-(4-acetylphenyl) Examples include 1,7-(9,9'-acridinyl)acridine, 9-(4-chlorophenyl)acridine, 9-(4-bromophenyl)acridine, 9-(3-methylphenyl)acridine, 9-(3-tert-butylphenyl)acridine, 9-(3-acetylphenyl)acridine, 9-(3-dimethylaminophenyl)acridine, 9-(3-diethylaminophenyl)acridine, 9-(3-chlorophenyl)acridine, 9-(3-bromophenyl)acridine, 9-(2-pyridyl)acridine, 9-(3-pyridyl)acridine, and 9-(4-pyridyl)acridine. Among these, 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine are preferred in terms of sensitivity, resolution, and availability.

[0087] N-aryl-α-amino acid compounds are preferred from the viewpoint of improving sensitivity. Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

[0088] Further examples of photopolymerization initiators include, for example, quinones such as 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantraquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzyl derivatives such as benzyl methyl ketal; and coumarin compounds. Examples include pyrazoline derivatives such as 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, and 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline.

[0089] Among these, it is preferable to include a triarylimidazole dimer as a photopolymerization initiator. When a triarylimidazole dimer is included as a photopolymerization initiator, the content of the triarylimidazole dimer in the photosensitive resin composition is preferably 0.3% to 10% by mass, more preferably 1% to 5% by mass, even more preferably 1% to 3% by mass, and most preferably 1% to 2% by mass, based on the total solid content mass of the photosensitive resin composition or photosensitive resin layer.

[0090] When the content of triarylimidazole dimer in the photosensitive resin composition is within the above range, the content of other photopolymerization initiators is preferably 0% by mass or more and 0.20% by mass or less, and more preferably 0% by mass or more and 0.10% by mass or less.

[0091] <Sensitizer> The photosensitive resin composition and the photosensitive resin layer may each further contain a sensitizer. In this specification, the sensitizer refers to a compound that exhibits a sensitizing effect when used in combination with a photopolymerization initiator. Examples of sensitizers include pyrazoline derivatives, anthracene derivatives, triarylamine derivatives, oxazole derivatives, N-aryl-α-amino acid derivatives other than oxazole derivatives, aromatic ketone derivatives substituted with alkylamino groups, dialkylaminobenzoic acid ester derivatives, and coumarin derivatives.

[0092] Examples of pyrazoline derivatives include 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-(4-(benzoxazole-2-yl)phenyl)-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)-pyrazoline, and 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxy Examples include phenyl)-pyrazoline, 1-phenyl-3-(3,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, and 1-phenyl-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline. Among these, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline is preferred.

[0093] Examples of anthracene derivatives include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 2-ethyl-9,10-dibutoxyanthracene, 9-bromo-10-phenylanthracene, and 9-chloro-10-phenyl Examples include anthracene, 9-bromo-10-(2-naphthyl)anthracene, 9-bromo-10-(1-naphthyl)anthracene, 9-(2-biphenylyl)-10-bromoanthracene, 9-(4-biphenylyl)-10-bromoanthracene, 9-bromo-10-(9-phenanthryl)anthracene, 2-bromoanthracene, 9-bromoanthracene, 2-chloroanthracene, 9,10-dibromoanthracene, 9-(3-bromophenyl)-10-phenylanthracene, and 10-phenyl-9-anthraceneboronic acid. Among these, 9,10-diphenylanthracene or 10-phenyl-9-anthraceneboronic acid are preferred from the viewpoint of adhesion.

[0094] Examples of oxazole derivatives include 5-tert-butyl-2-[5-(5-tert-butyl-1,3-benzoxazole-2-yl)thiophen-2-yl]-1,3-benzoxazole and 2-[4-(1,3-benzoxazole-2-yl)naphthalene-1-yl]-1,3-benzoxazole.

[0095] Examples of N-aryl-α-amino acid derivatives include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, N-(n-propyl)-N-phenylglycine, N-(n-butyl)-N-phenylglycine, N-(2-methoxyethyl)-N-phenylglycine, N-methyl-N-phenylalanine, N-ethyl-N-phenylalanine, N-(n-propyl)-N-phenylalanine, N-(n-butyl)-N-phenylalanine, N-methyl-N-phenylvaline, N-methyl-N-phenylleucine, N-methyl-N-(p-tolyl)glycine, N-ethyl-N-(p-tolyl)glycine, and N-(n-propyl Examples include N-(p-tolyl)glycine, N-(n-butyl)-N-(p-tolyl)glycine, N-methyl-N-(p-chlorophenyl)glycine, N-ethyl-N-(p-chlorophenyl)glycine, N-(n-propyl)-N-(p-chlorophenyl)glycine, N-methyl-N-(p-bromophenyl)glycine, N-ethyl-N-(p-bromophenyl)glycine, N-(n-butyl)-N-(p-bromophenyl)glycine, N,N'-diphenylglycine, N-methyl-N-(p-iodophenyl)glycine, N-(p-bromophenyl)glycine, N-(p-chlorophenyl)glycine, and N-(o-chlorophenyl)glycine. N-phenylglycine is particularly preferred due to its high sensitizing effect.

[0096] Examples of aromatic ketone derivatives include benzophenone and aromatic ketone derivatives substituted with alkylamino groups. Aromatic ketone derivatives substituted with alkylamino groups are particularly preferred due to their high sensitizing effect. Examples of aromatic ketone derivatives substituted with alkylamino groups include benzophenone derivatives, specifically alkylbenzophenone compounds such as benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, or 4-methylbenzophenone; benzophenone compounds having halogen atoms such as 2-chlorobenzophenone, 4-chlorobenzophenone, or 4-bromobenzophenone; and carboxyl groups such as 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenone tetracarboxylic acid, or its tetramethyl ester. Examples include benzophenone compounds substituted with an alkoxycarbonyl group, bis(dialkylamino)benzophenone compounds such as 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(dicyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dihydroxyethylamino)benzophenone (preferably 4,4'-bis(dialkylamino)benzophenone compounds), 4-methoxy-4'-dimethylaminobenzophenone, 4-methoxybenzophenone, and 4,4'-dimethoxybenzophenone. Among these, 4,4'-bis(diethylamino)benzophenone is preferred from the viewpoint of adhesion. The sensitizer preferably contains anthracene derivatives, pyrazoline derivatives, or benzophenone derivatives from the viewpoint of adhesion.

[0097] The above-mentioned sensitizers may be used alone or in combination of two or more.

[0098] The amount of sensitizer contained in the photosensitive resin composition and the photosensitive resin layer is preferably 0.05% by mass or less, more preferably 0.01% by mass or less, and even more preferably 0.005% by mass or less, based on the total mass of the photosensitive resin layer.

[0099] By setting the content of the sensitizer contained in the photosensitive resin composition and the photosensitive resin layer to a predetermined range, the transmittance of the photosensitive resin layer is improved, light reaches the bottom of the thick resist during exposure, curability is enhanced, and in the resist pattern formation method described later, a resist pattern containing circular hole portions with an aspect ratio of 2.5 or more, preferably 3.0 or more, more preferably 4.0 or more, and even more preferably 6.0 or more can be suitably formed.

[0100] Furthermore, the lower limit of the sensitizer content is preferably 0% by mass.

[0101] <Dyes> The photosensitive resin composition and the photosensitive resin layer may each further contain dyes. The dyes may include at least one selected from leuco dyes, fluorane dyes, and other coloring substances. The inclusion of these components in the photosensitive resin layer causes the exposed areas to develop color, improving visibility. Furthermore, when an inspection machine or the like reads the alignment marker for exposure, the contrast between the exposed and unexposed areas increases, making them easier to recognize.

[0102] Examples of leuco dyes include tris(4-dimethylaminophenyl)methane [leucocrystal violet] and bis(4-dimethylaminophenyl)phenylmethane [leucomalachite green]. From the viewpoint of good contrast, leucocrystal violet is preferred as the leuco dye.

[0103] Examples of fluorane dyes include 2-(dibenzylamino)fluorane, 2-anilino-3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-dibutylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N-isoamylaminofluorane, 2-anilino-3-methyl-6-N-methyl-N-cyclohexylaminofluorane, 2-anilino-3-chlor-6-diethylaminofluorane, and 2-ani Examples include lino-3-methyl-6-N-ethyl-N-isobutylaminofluorane, 2-anilino-6-dibutylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N-tetrahydrofurfurylaminofluorane, 2-anilino-3-methyl-6-piperidinoaminofluorane, 2-(o-chloroanilino)-6-diethylaminofluorane, and 2-(3,4-dichloroanilino)-6-diethylaminofluorane.

[0104] The amount of leuco dye or fluoran dye in the photosensitive resin composition and the photosensitive resin layer is preferably 0.1% to 10% by mass, more preferably 0.2% to 5% by mass, and even more preferably 0.3% to 1% by mass, based on the total solid content mass of the photosensitive resin composition and the photosensitive resin layer, respectively. When the amount of the dye is 0.1% by mass or more, the contrast between the exposed and unexposed areas tends to improve. When the amount of the dye is 10% by mass or less, the storage stability of the photosensitive resin layer improves and the occurrence of aggregates during development tends to be suppressed.

[0105] Examples of coloring substances include fuchsin, phthalocyanine green, auramine base, paramazienta, crystal violet, methyl orange, Nile Blue 2B, malachite green (manufactured by Hodogaya Chemical Co., Ltd., Eisen® MALACHITE GREEN), Basic Blue 7 (e.g., Eisen® Victoria Pure Blue BOH conc.), Basic Blue 20, and Diamond Green (manufactured by Hodogaya Chemical Co., Ltd., Eisen® DIAMOND GREEN GH).

[0106] The amount of coloring substance in the photosensitive resin composition and the photosensitive resin layer is preferably 0.001% by mass to 1% by mass, based on the total solid content mass of the photosensitive resin composition and the photosensitive resin layer, respectively. When the amount of coloring substance is 0.001% by mass or more, the contrast improves, and when it is 1% by mass or less, the storage stability tends to improve.

[0107] <Halogen Compounds> The photosensitive resin composition and the photosensitive resin layer may each further contain halogen compounds, and it is preferable that they further contain halogen compounds in combination with leuco dyes. When a combination of leuco dyes and halogen compounds is included, adhesion and contrast tend to improve.

[0108] Examples of halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, and chlorinated triazine compounds. Among these, tribromomethylphenylsulfone is preferred as the halogen compound. Halogen compounds such as tribromomethylphenylsulfone are particularly effective when used in combination with acridine compounds as photopolymerization initiators, and are preferred from the viewpoints of improving resolution, adhesion, sensitivity, contrast, tent film puncture resistance, suppression of resist trimming, and etching resistance.

[0109] From the viewpoint of the above, the content of halogen compounds in the photosensitive resin composition and the photosensitive resin layer is preferably 0.01% by mass or more, based on the total solid content mass of the photosensitive resin composition and the photosensitive resin layer, respectively. More preferably, this content is 0.1% by mass or more, even more preferably 0.3% by mass or more, and particularly preferably 0.5% by mass or more. Furthermore, a content of 3% by mass or less is preferable from the viewpoint of maintaining the storage stability of hue in the photosensitive resin layer and suppressing the generation of aggregates during development. More preferably, this content is 2% by mass or less, and even more preferably 1.5% by mass or less.

[0110] <Antioxidants> The photosensitive resin composition and the photosensitive resin layer may each further contain antioxidants. Antioxidants can improve the thermal stability and storage stability of the photosensitive resin layer. As antioxidants, at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles is preferred.

[0111] Examples of radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, phenothiazine, biphenol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), and 4,4'-thiobis(6-tert-butyl-m-cresol). Examples include zole, 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, styrene-phenols (e.g., manufactured by Kawaguchi Chemical Industries, Ltd., trade name "Antage SP"), tripenzylphenols (e.g., manufactured by Kawaguchi Chemical Industries, Ltd., trade name "TBP", phenol compounds having 1 to 3 benzyl groups), and diphenylnitrosamines.

[0112] Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0113] Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole, and mixtures thereof. Among these, a mixture of 4-carboxy-1,2,3-benzotriazole and 5-carboxy-1,2,3-benzotriazole is preferred, with a preferred mixing ratio of approximately 1:1 by mass.

[0114] The total content of antioxidants is preferably 0.01% to 3% by mass, and more preferably 0.05% to 1% by mass, based on the total solid content mass of the photosensitive resin composition or photosensitive resin layer. When the amount of antioxidant is 0.01% by mass or more, the storage stability of the photosensitive resin layer is enhanced, and when it is 3% by mass or less, sensitivity is maintained and dye decolorization tends to be suppressed.

[0115] <Plasticizers> The photosensitive resin composition or photosensitive resin layer may contain plasticizers as needed. Examples of plasticizers include glycol esters such as polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, and polyoxyethylene polyoxypropylene monoethyl ether; phthalate esters such as diethyl phthalate; o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, and tri-n-butyl acetyl citrate; propylene glycol obtained by adding propylene oxide to both ends of bisphenol A, ethylene glycol obtained by adding ethylene oxide to both ends of bisphenol A, etc.; aluminum salts to which 1 to 3 moles of nitrosophenylhydroxylamine have been added, etc. These can be used individually or in combination of two or more. Among these, aluminum salts with 3 moles of nitrosophenylhydroxylamine added are preferred from the viewpoint of resistance to plating penetration.

[0116] The amount of plasticizer in the photosensitive resin composition and the photosensitive resin layer is preferably 1% to 50% by mass, and more preferably 1% to 30% by mass, based on the total solid content mass of the photosensitive resin composition and the photosensitive resin layer, respectively. When the amount of plasticizer is 1% by mass or more, the delay in development time is suppressed and flexibility is imparted to the cured film, while when it is 50% by mass or less, insufficient curing and edge fusing tend to be suppressed.

[0117] <Solvent> The photosensitive resin layer can be formed by applying a solution of each component dissolved in a solvent onto a support film, as described later, and then drying it. The photosensitive resin composition according to this embodiment may optionally contain a solvent in addition to the above-mentioned components. The resulting photosensitive resin layer may also contain residual solvent. Examples of solvents include ketones represented by methyl ethyl ketone (MEK), alcohols represented by methanol, ethanol, and isopropanol, etc.

[0118] <Film Thickness> The film thickness of the photosensitive resin layer is 100 μm or more, preferably exceeding 110 μm, and more preferably 115 μm or more. In plating processes, a photosensitive resin laminate having a thick (in one embodiment, 100 μm or more) photosensitive resin layer may be used. Furthermore, a thicker photosensitive resin layer suppresses the generation of lamination air, making it possible to obtain a photosensitive resin laminate suitable for plating processes that form, for example, metal pillars. The lower limit of the film thickness of the photosensitive resin layer may be 200 μm or more, 300 μm or more, or 400 μm or more. The upper limit of the film thickness of the photosensitive resin layer is not limited, but for example, it can be 1000 μm or less, 800 μm or less, or 500 μm or less.

[0119] <Optical Properties> The transmittance of the photosensitive resin layer at a wavelength of 365 nm according to this disclosure is preferable as a higher value improves the resolution of the resist pattern, more preferably 10% or more, even more preferably 20% or more, even more preferably 30% or more, and particularly preferably 50% or more. From a similar viewpoint, the transmittance of the photosensitive resin layer at a wavelength of 405 nm is also preferable as a higher value increases, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and particularly preferably 80% or more.

[0120] Furthermore, in the photosensitive resin laminate of the present disclosure, the ratio A / T of the absorbance (A) at 365 nm of the photosensitive resin layer to the film thickness (T) [μm] is preferably 0.003 or less, more preferably 0.0025 or less, and even more preferably 0.002 or less.

[0121] Methods for controlling the ratio A / T of absorbance (A) to film thickness (T) [μm] at 365 nm of the photosensitive resin layer to 0.003 or less include, but are not limited to, the following: setting the content of an imidazole compound as a photopolymerization initiator to 1% to 3% by mass, based on the total solid content mass of the photosensitive resin composition; and setting the content of sensitizers such as pyrazoline derivatives, anthracene derivatives, triarylamine derivatives, oxazole derivatives, N-aryl-α-amino acid derivatives other than oxazole derivatives, aromatic ketone derivatives substituted with alkylamino groups, dialkylaminobenzoic acid ester derivatives, and coumarin derivatives to 0.005% by mass or less.

[0122] This improves the resolution of the resist pattern, particularly the curability of the resist bottom, and makes it easier to improve the properties related to the bottom length of the resist pattern. Regarding the resolution of the resist pattern, for example, in the resist pattern formation method described later, it is possible to suitably form a resist pattern including circular hole portions with an aspect ratio of 2.5 or more, preferably 3.0 or more, more preferably 4.0 or more, and even more preferably 6.0 or more. In particular, good rectangularity and resolution can be obtained when using an exposure machine that uses i-line (wavelength 365 nm) as a light source.

[0123] Furthermore, the lower limit of A / T is greater than 0, preferably 0.0005 or higher.

[0124] <Development Speed> In the photosensitive resin laminate of the present disclosure, the development speed of the photosensitive resin layer is preferably 0.25 μm / s or more and 3.00 μm / s or less, more preferably 0.50 μm / s or more and 2.00 μm / s or less, and even more preferably 1.00 μm / s or more and 1.50 μm / s or less.

[0125] This makes it possible to suppress residue after development caused by low developability and swelling caused by high developability, and in the resist pattern formation method described later, it is possible to suitably form a resist pattern including circular hole portions with an aspect ratio of 2.5 or more, preferably 3.0 or more, more preferably 4.0 or more, and even more preferably 6.0 or more.

[0126] In this disclosure, the development speed of the photosensitive resin layer is a value obtained by dividing the thickness (T) of the photosensitive resin layer, measured in the method shown in the examples described later, by the minimum development time.

[0127] <Support Film> The support film should preferably be transparent and transmit light emitted from the exposure light source. Examples of support films include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. These films can also be used in stretched form as needed. The haze of the support film should preferably be 5% or less, more preferably 1% or less, even more preferably 0.5% or less, and most preferably 0.3% or less. A thinner support film is advantageous in terms of image formation and cost-effectiveness, but considering the function of maintaining strength, a thickness of 10 μm or more is preferable. Furthermore, if the photosensitive resin layer is 80 μm or thicker, that is, if the photosensitive resin layer is a thick film, the support film is preferably thicker from the viewpoint of film thickness stability during coating. Specifically, the support film is preferably 20 μm or thicker, more preferably 50 μm or thicker, even more preferably 75 μm or thicker, and most preferably 100 μm or thicker. From the viewpoint of slitting processability, the support film may be 500 μm or less.

[0128] Furthermore, the thickness of the support film may be 10% or more of the thickness of the photosensitive resin layer, and may also be 20% or more.

[0129] <Protective Layer> The photosensitive resin laminate may have a protective layer on the surface opposite to the support film of the photosensitive resin layer. The protective layer plays a role in protecting the photosensitive resin layer. It is preferable that the protective layer has appropriate adhesion to the photosensitive resin layer. That is, it is preferable that the adhesion of the protective layer to the photosensitive resin layer is sufficiently smaller than the adhesion of the support film to the photosensitive resin layer, so that the protective layer can be easily peeled off the photosensitive resin laminate. As the protective layer, for example, polyethylene film, polypropylene film, or a film with excellent peelability as shown in Japanese Patent Publication No. 59-202457 can be used. The thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 to 50 μm.

[0130] 《Method for Manufacturing a Photosensitive Resin Laminate》 A photosensitive resin laminate can be manufactured by sequentially laminating a photosensitive resin layer and, if necessary, a protective layer on a support film. Known methods can be used for lamination. For example, each component used in the photosensitive resin layer is mixed with a solvent to dissolve them and obtain a uniform solution (coating solution). Examples of solvents include ketones represented by methyl ethyl ketone (MEK), methanol, ethanol, and alcohols represented by isopropanol. The amount of solvent is preferably such that the viscosity of the coating solution is 500 to 6,000 mPa·s at 25°C. The coating solution can be applied to the support film and then dried to form a photosensitive resin layer on the support film. Known methods can be used for application, for example, by using a bar coater or a roll coater. Then, if necessary, a protective layer is laminated onto the photosensitive resin layer to manufacture a photosensitive resin laminate.

[0131] 《Method for forming a resist pattern, a method for forming a metal pillar, and a method for forming a semiconductor bump》 Using the photosensitive resin laminate of this disclosure, a resist pattern including circular hole portions with an aspect ratio of 2.5 or more can be formed.

[0132] In this specification, the aspect ratio represents the ratio of film thickness to hole diameter (film thickness / hole diameter). In this specification, if the shape of the hole portion on the outermost surface opposite to the substrate side in the film thickness direction of the resist pattern is substantially circular, that is, if the ratio of the diameters of the inscribed circle to the circumscribed circle of the hole portion on the outermost surface opposite to the substrate side in the film thickness direction of the resist pattern is 1.1 or less, the resist pattern may be considered to include a hole portion. In this specification, the hole diameter represents the diameter of the hole portion on the outermost surface opposite to the substrate side in the film thickness direction of the resist pattern. If the shape of the hole portion on the outermost surface opposite to the substrate side in the film thickness direction of the resist pattern is substantially circular, the hole diameter is defined as the average value of the diameters of the inscribed circle and the circumscribed circle of the cross-section of the hole portion parallel to the substrate.

[0133] The resist pattern formation method of the present disclosure is a method for forming a resist pattern including a circular hole portion having an aspect ratio of 2.5 or more, and comprises: (1) a step of laminating a photosensitive resin laminate including a support film and a photosensitive resin layer having a thickness of 100 μm or more onto a substrate (laminating step); (2) a step of exposing the laminated photosensitive resin layer (exposure step); and (3) a step of developing and removing the unexposed portion of the photosensitive resin layer after exposure (development step). In the present disclosure, the photosensitive resin layer contains an alkali-soluble polymer containing a monomer having an aromatic ring as a copolymer component, the development speed of the photosensitive resin layer is 0.25 μm / s or more and 3.00 μm / s or less at the minimum development time of the photosensitive resin layer consisting only of the unexposed portion, and the development time in step (3) is 2.5 times or more the minimum development time of the photosensitive resin layer consisting only of the unexposed portion.

[0134] Thus, in the resist pattern formation method of the present disclosure, by optimizing the combination of exposure conditions and development conditions for the photosensitive resin layer, the developability and resolution of the photosensitive resin layer can be improved, and a resist pattern including circular hole portions with an aspect ratio of 2.5 or more can be formed.

[0135] Furthermore, the resist pattern formation method of this disclosure may optionally include a step of heating the obtained resist pattern (heating step).

[0136] Metal pillars or semiconductor bumps can be formed using a substrate on which a resist pattern has been formed. The method for forming metal pillars or semiconductor bumps may optionally include: a descam and pre-plating treatment step; a step of forming metal pillars or semiconductor bumps by metal plating or solder plating the substrate on which the resist pattern has been formed (plating step); an optional step of etching the substrate on which the resist pattern has been formed (etching step); and an optional step of peeling the resist pattern from the substrate (peeling step).

[0137] The following describes a series of methods for forming resist patterns and metal pillars or semiconductor bumps using a photosensitive resin laminate and a sputtered copper thin film as a substrate.

[0138] (1) Lamination process: For example, while peeling off the protective layer of the photosensitive resin laminate, the laminate is pressed onto a substrate such as a sputtered copper thin film using, for example, a hot roll laminator or a vacuum laminator. The sputtered copper thin film is preferably a copper sputtered silicon wafer in which a copper layer has been formed on a silicon wafer using a sputtering apparatus.

[0139] (2) Exposure process The exposure process may be, for example: a process of exposing the photosensitive resin layer of a photosensitive resin laminate laminated on the substrate to a mask film having a desired wiring pattern while the mask film is in close contact with the photosensitive resin layer, a process of exposing the desired wiring pattern by direct imaging exposure, or a process of exposing the photosensitive resin layer by projecting the image of a photomask through a lens.

[0140] In the resist pattern formation method of the present disclosure, exposure is performed in the exposure step using a projection exposure machine equipped with a lens having a numerical aperture (NA) of 0.16 or less, more preferably a lens having a numerical aperture (NA) of 0.10 or less.

[0141] This widens the focus range in the depth direction, making it possible to achieve high resolution even at the bottom of the holes, and allows for the suitability of forming a resist pattern that includes circular hole portions with an aspect ratio of 2.5 or higher, preferably 3.0 or higher, more preferably 4.0 or higher, and even more preferably 6.0 or higher.

[0142] Furthermore, while there are no particular limitations on the lower limit of the numerical aperture, for example, it is 0.01 or higher.

[0143] Furthermore, while the i-line (365 nm) is a typical example of an exposure wavelength, exposure can also be performed using light that has a maximum light intensity between wavelengths of 350 nm and 410 nm.

[0144] (3) Development process After the exposure process, the support film on the photosensitive resin layer is peeled off, and the unexposed areas (in the case of negative type) or exposed areas (in the case of positive type) are developed and removed using an alkaline aqueous developer to form a resist pattern on the substrate. The development method can be appropriately selected from conveyor type, spin type, spray type, or dip type development methods.

[0145] Furthermore, in the resist pattern formation method of this disclosure, the development time is 2.5 times or more the minimum development time for the photosensitive resin layer consisting only of the unexposed portion, preferably 3.0 times or more, and more preferably 4.0 times or more.

[0146] When the development time is extended beyond the minimum development time of the photosensitive resin layer (for example, by 3.0 times or more, 4.0 times or more, or up to the upper limit), it is preferable to suppress the penetration of the developer into the exposed area of ​​the photosensitive resin layer. Means for suppressing the penetration of the developer into the exposed area of ​​the photosensitive resin layer include (A) ensuring that the content of monomers having aromatic rings as copolymer components in the alkali-soluble polymer contained in the photosensitive resin layer is 40% by mass or more, and (B) including a compound having an ethylenically unsaturated bond in which both ends of bisphenol A are modified with EO and acryloyl groups at both ends.

[0147] By extending the development time, the resist at the bottom dissolves, enabling resolution even for small holes, and allowing for the suitable formation of a resist pattern containing circular hole portions with an aspect ratio of 2.5 or higher, preferably 3.0 or higher, more preferably 4.0 or higher, and even more preferably 6.0 or higher.

[0148] Furthermore, the upper limit of the development time is preferably 10 times the minimum development time, and more preferably 6.0 times. The minimum development time can be determined by measuring the shortest time it takes for the unexposed photosensitive resin layer to completely dissolve using the development conditions used for resist pattern formation. In addition, when suitably forming a resist pattern that includes circular hole portions with an aspect ratio of 4.0 or more or 6.0 or more, the development time may be longer than the minimum development time when the aspect ratio is 2.5 or more. For example, when suitably forming a resist pattern that includes circular hole portions with an aspect ratio of 4.0 or more or 6.0 or more, the upper limit of the development time may be 50 times or 30 times the minimum development time.

[0149] As for alkaline aqueous solutions, Na ２ CO ３ or K ２ CO ３ Alternatively, an aqueous solution of an organic amine compound such as TMAH (tetramethylammonium hydroxide) can be used. The alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, but it should have a concentration of about 0.2 to 2% by mass and be at about 20 to 40°C. ２ CO ３ It is preferable to use an aqueous solution.

[0150] The conditions for the exposure and / or development process may be determined according to the desired shape of the metal pillar or semiconductor bump. For example, in the case of forming metal pillars such as metal cylinders or polygonal prism patterns, the exposure and / or development process may be carried out in such a way that a hole-type resist pattern can be formed in which the ratio of the hole diameter to the film thickness of more than 100 μm is relatively high.

[0151] Thus, in the pattern forming method of the present disclosure, by performing steps (1) to (3) above, a resist pattern including circular hole portions with an aspect ratio of 2.5 or more, preferably 3.0 or more, more preferably 4.0 or more, and even more preferably 6.0 or more can be formed on the photosensitive resin layer.

[0152] In particular, in the pattern forming method of the present disclosure, (2) in the exposure step, exposure is performed using a projection exposure machine equipped with a lens having a numerical aperture (NA) of 0.16 or less, and (3) in the development step, 1% by mass of Na as the developer. ２ CO ３ By performing steps (1) to (3) using an aqueous solution and setting the development time to 2.5 times the minimum development time for a photosensitive resin layer consisting only of unexposed areas, it is possible to form a resist pattern in the photosensitive resin layer that includes circular hole portions with an aspect ratio of 3.0 or greater.

[0153] Furthermore, in the pattern forming method of the present disclosure, (2) in the exposure step, exposure is performed using a projection exposure machine equipped with a lens having a numerical aperture (NA) of 0.16 or less, and (3) in the exposure step, 1% by mass of Na as the developer. ２ CO ３ By performing steps (1) to (3) using an aqueous solution and setting the development time to 3.0 times the minimum development time for a photosensitive resin layer consisting only of unexposed areas, it is possible to form a resist pattern in the photosensitive resin layer that includes circular hole portions with an aspect ratio of 4.0 or more.

[0154] (4) Heating step If desired, the formed resist pattern may be further heated for 1 minute to 5 hours at, for example, about 50°C to 300°C. By performing this heating step, the adhesion and chemical resistance of the resulting cured resist pattern can be further improved. For heating in this case, for example, a heating furnace using a hot plate, hot air, infrared rays, or far infrared rays can be used.

[0155] (5) Descam and pre-plating treatment If desired, the substrate on which the resist pattern has been formed may be subjected to plasma treatment and / or immersion treatment to perform descam and pre-plating treatment.

[0156] Furthermore, in the resist pattern formation method of the present disclosure, by performing the following steps in order: (6) a step of plating metal (for example, copper) onto the circular hole portions on the substrate with an aspect ratio of 3.0 or more obtained as described above (plating step), and (7) a step of peeling off the portions of the photosensitive resin layer that were exposed in the exposure step (peeling step), a metal (copper) pillar pattern with an aspect ratio of 2.7 or more can be formed.

[0157] (6) Plating process Metal plating is applied to the circular hole portions on the substrate with an aspect ratio of 3.0 or more. Conductor patterns can be manufactured by metal plating the substrate surface exposed by development (for example, the copper surface of a sputtered copper thin film). The metal plating is preferably copper plating, and the plating solution is preferably copper sulfate plating solution.

[0158] (7) Peeling step The portion of the photosensitive resin layer exposed in (2) exposure step is peeled off. The laminate is then treated with an aqueous solution having a stronger alkalinity than the developer to peel off the resist pattern from the substrate. Examples of peeling solutions include an aqueous solution of an alkaline component with a concentration of about 2 to 5% by mass and a temperature of about 40 to 70°C; an aqueous solution of NaOH or KOH; dimethyl sulfoxide (DMSO); tetramethylammonium hydroxide (TMAH); a mixture of DMSO and TMAH; SPR920 (product name); R-101 (product name); and a peeling solution that does not contain DMSO (hereinafter referred to as "DMSO-free peeling solution"). Among these, a DMSO-free peeling solution is preferred from the viewpoint of the effects of the photosensitive resin laminate according to this disclosure and from the viewpoint of reducing environmental burden. A DMSO-free peeling solution may contain one or more of the above components other than DMSO.

[0159] In this manner, the method of the present disclosure can form a metal (copper) pillar pattern with an aspect ratio of 2.7 or higher, preferably 3.0 or higher, more preferably 3.5 or higher, even more preferably 4.5 or higher, and particularly preferably 5.5 or higher.

[0160] The photosensitive resin laminates, resist patterns, metal (copper) pillars, and semiconductor bumps described above can be used, for example, in the formation of semiconductor packages and wafer-level packages (WLPs).

[0161] [Examples 1-20 and Comparative Examples 1-5] <Preparation of Photosensitive Resin Laminates> The materials shown in Tables 1 and 2 below were stirred and mixed in the compositions shown in Tables 3-1, 3-2, and 4 (however, the numbers for each component indicate the amount (parts by mass) of solids) to obtain a photosensitive resin coating solution. The obtained coating solution was uniformly applied to the surface of a 16 μm thick polyethylene terephthalate film (Toray Industries, Inc., FB-40) as a support film using a bar coater, and dried in a dryer at 95°C to form a photosensitive resin layer having the film thickness (T) [μm] described in Tables 3-1, 3-2, and 4. At this time, the drying time was set to T / 10 [min] using the film thickness (T) [μm].

[0162] A photosensitive resin laminate (photosensitive element) was obtained by laminating a 19 μm thick polyethylene film (GF-18, manufactured by Tamapoly Co., Ltd.) as a protective layer onto a surface where the support film for the photosensitive resin layer was not laminated.

[0163] [Measurement and Evaluation] <Absorbance (A) / Film Thickness (T) at a wavelength of 365 nm> After peeling off the protective film of the above photosensitive laminate, the absorbance (A) of the photosensitive resin layer at a wavelength of 365 nm was measured using a spectrophotometer U-3010 (manufactured by Hitachi High-Technologies Corporation) with polyethylene terephthalate film (support film) as a reference. The measurement was performed with a slit of 4 nm and a scan speed of 600 nm / min. By dividing this absorbance (A) by the film thickness (T) [μm], the absorbance (A) / film thickness (T) values ​​of the photosensitive resin layer at 365 nm shown in Tables 3-1, 3-2, and 4 were obtained.

[0164] <Minimum Development Time> As a substrate, a 6-inch silicon wafer was prepared with a 2000 angstrom (Å) thick copper layer formed on it using a Canon Anelva sputtering apparatus (L-440S-FHL) (copper sputtered silicon wafer). While peeling the polyethylene film from the photosensitive element, the silicon wafer was laminated using an air damper type hot roll laminator (Taisei Laminator Co., Ltd., VA-400III) on a wafer preheated to 70°C at a roll temperature of 70°C. The air pressure was set to 0.20 MPa and the lamination speed to 0.18 m / min. After peeling the support film from the wafer, a spin developer (Takizawa Sangyo Co., Ltd., spin developer AD-1200) was used to develop 1 mass% Na ２ CO ３ An aqueous solution was sprayed onto a photosensitive resin layer at a liquid temperature of 30°C and a flow rate of 200 mL / min (spray development). For each experimental example, the shortest time required for the unexposed photosensitive resin layer to completely dissolve under the above conditions was defined as the "minimum development time." A smaller "minimum development time" value indicates better performance. Furthermore, the development speed (μm / sec) for each experimental example was obtained by dividing the thickness (T) of the photosensitive resin layer by the minimum development time.

[0165] <Evaluation Substrate> <Substrate> As the substrate, a 6-inch silicon wafer was prepared by forming a copper layer with a thickness of 2000 angstroms (Å) on it using a sputtering apparatus (L-440S-FHL) manufactured by Canon Anelva Corporation (copper sputtered silicon wafer).

[0166] <Lamination> While peeling the polyethylene film from the photosensitive element, the substrate, preheated to 70°C, was laminated using an air damper type hot roll laminator (Taisei Laminator Co., Ltd., VA-400III) at a roll temperature of 70°C. The air pressure was set to 0.20 MPa and the lamination speed to 0.18 m / min.

[0167] <Exposure (NA = 0.16)> A glass-chromium mask with circular hole patterns (patterns where the outside of the circle is exposed and the inside of the circle is not exposed to the photosensitive material) arranged at intervals of 5 μm from a diameter of 10 μm to 100 μm was prepared. Using this glass-chromium mask, the substrate after the above <Lamination> was exposed with an Ultratech Prisma ghi stepper (manufactured by Ultratech, NA = 0.16) at 200 mJ / cm ２ 2. The illuminance measured on the substrate surface was 2400 mW / cm ２ . The evaluation conditions and evaluation results on the above exposure machine are summarized in Tables 3-1 and 3-2.

[0168] <Exposure (NA = 0.10)> A glass-chromium mask with circular hole patterns (patterns where the outside of the circle is exposed and the inside of the circle is not exposed to the photosensitive material) arranged at intervals of 5 μm from a diameter of 10 μm to 100 μm was prepared. Using this glass-chromium mask, the substrate after the above <Lamination> was exposed with a PPS-8300 (manufactured by Okou Seisakusho, stepper, NA = 0.10, ghi-line exposure) at 200 mJ / cm ２ . The evaluation conditions and evaluation results on the above exposure machine are summarized in Table 4.

[0169] <Development> The PET film was peeled off from the substrate after the above <Exposure>, and then, using a spin developer (Spin Developer AD-1200 manufactured by Takizawa Sangyo Co., Ltd.), an aqueous solution of 1 mass% Na ２ CO ３ was sprayed onto the photosensitive resin layer under the conditions of a liquid temperature of 30°C and a flow rate of 200 mL / min (spray development). Each experimental example was developed for the development time described in Tables 3-1, 3-2, and 4. After development, water was sprayed onto the photosensitive resin layer (water wash spray). The conditions and time of the water wash spray were set the same as those of the development spray.

[0170] [Evaluation Method] <Resolution> The resist pattern formed after <exposure> and <development> was observed at 10x magnification using an optical microscope. The resolution was evaluated by the value of the diameter (μm) of the mask pattern in the area where the mask pattern diameter was smallest among the areas where the space (unexposed area) was completely removed without residue. A smaller value indicates better resolution.

[0171] <Trim Length> The above <Development> procedure was performed using a circular hole pattern with an aspect ratio of 3.0 (for example, a diameter of 40 μm for a film thickness of 120 μm). After that, the wafer on which the resist pattern was formed was cut, and the cross-sectional shape of the resist pattern was observed at the bottom of the circular hole using a scanning electron microscope (Hitachi High-Technologies Corporation, S-3400N) to observe the length of the resist trim. A shorter resist trim indicates better performance, and a trim length shorter than 15 μm was considered acceptable. In the resist patterns of Comparative Examples 2 and 3, the aspect ratio was less than 3.0, so even when development was performed using a circular hole pattern with an aspect ratio of 3.0, the entire resist pattern was not resolved, and the length of the resist trim could not be observed.

[0172] <Plating Formability> The substrate, which had been processed up to the <development> stage under the conditions of Example 16, was subjected to low-pressure plasma treatment using a low-pressure plasma device (Shinko Seiki Co., Ltd., EXAM) at 50 Pa, 133 W, O ２ 40mL / min, CF ４Plasma treatment was performed on the resist pattern under the conditions of 1 mL / min and 1500 sec (Descam treatment and pre-plating treatment). Then, 968 mL of SC-50 MU MA (manufactured by MICROFAB®), 20 mL of SC-50 R1 (manufactured by the same company), and 12 mL of SC-50 R2 (manufactured by the same company) were mixed to obtain a copper sulfate plating solution. Using the obtained copper sulfate plating solution, the substrate (6 cm × 12.5 cm) that had undergone the above-mentioned <Descam treatment and pre-plating treatment> was copper plated using a Harling cell uniform plating apparatus (manufactured by Yamamoto Plating Tester Co., Ltd.). Here, the current value was adjusted so that copper was deposited at a height (thickness) of 1 μm per minute. As a result, a copper plating film of 100 μm was obtained. This substrate was immersed in SPR920 (manufactured by KANTO-PPC) stripping solution at 68°C for 30 minutes. The substrate was then washed with water and air-dried. This removed the resist pattern, resulting in a substrate with a pattern of copper pillars with a diameter of 20 μm and a height of 100 μm.

[0173]

[0174]

[0175]

[0176]

[0177]

[0178] As is clear from Tables 3-1, 3-2, and 4, the examples successfully formed patterns with short trailing edges and high aspect ratios. In contrast, the comparative examples had long trailing edges and the aspect ratio of the resulting patterns was not sufficient.

Claims

1. A method for forming a resist pattern including a circular hole portion with an aspect ratio of 2.5 or more, comprising: (1) a step of laminating a photosensitive resin laminate including a support film and a photosensitive resin layer having a thickness of 100 μm or more onto a substrate; (2) a step of exposing the laminated photosensitive resin layer; and (3) a step of developing and removing the unexposed portion of the photosensitive resin layer after exposure, wherein the photosensitive resin layer contains an alkali-soluble polymer containing a monomer having an aromatic ring as a copolymer component, the development speed of the photosensitive resin layer is 0.25 μm / s or more and 3.00 μm / s or less at the minimum development time of the photosensitive resin layer consisting only of the unexposed portion, and the development time in step (3) is 2.5 times or more the minimum development time of the photosensitive resin layer consisting only of the unexposed portion.

2. The method for forming a resist pattern according to claim 1, wherein the ratio A / T of the absorbance (A) at 365 nm to the film thickness (T) [μm] of the photosensitive resin layer is 0.003 or less.

3. The method for forming a resist pattern according to claim 1, wherein the amount of sensitizer contained in the photosensitive resin layer is 0.005% by mass or less, based on the total mass of the photosensitive resin layer.

4. In step (3) above, Na as the developer ２ CO ３ A method for forming a resist pattern according to claim 1, using an aqueous solution.

5. The method for forming a resist pattern according to claim 1, wherein in step (2), exposure is performed using a projection exposure machine equipped with a lens having a numerical aperture (NA) of 0.16 or less.

6. The method for forming a resist pattern according to claim 1, wherein in step (2), exposure is performed using a projection exposure machine equipped with a lens having a numerical aperture (NA) of 0.10 or less.

7. The method for forming a resist pattern according to claim 1, wherein the formed resist pattern includes circular hole portions with an aspect ratio of 3.0 or more.

8. The photosensitive resin layer is exposed in step (2) using a projection exposure machine equipped with a lens having a numerical aperture (NA) of 0.16 or less, and in step (3) a developer solution containing 1% by mass of Na ２ CO ３ A method for forming a resist pattern according to claim 1, wherein, using an aqueous solution, the development time is set to 2.5 times the minimum development time for a photosensitive resin layer consisting only of unexposed areas, and a resist pattern including circular hole portions with an aspect ratio of 3.0 or more can be formed by steps (1) to (3).

9. The photosensitive resin layer is exposed in step (2) using a projection exposure machine equipped with a lens having a numerical aperture (NA) of 0.16 or less, and in step (3) a developer solution containing 1% by mass of Na ２ CO ３ A method for forming a resist pattern according to claim 1, wherein, using an aqueous solution, the development time is set to 3.0 times the minimum development time for a photosensitive resin layer consisting only of unexposed areas, and a resist pattern including circular hole portions with an aspect ratio of 4 or more can be formed by steps (1) to (3).

10. A method for forming a resist pattern according to claim 7, comprising, after steps (1) to (3), (6) a step of applying metal plating to the circular hole portion on the substrate having an aspect ratio of 3.0 or more; and (7) a step of peeling off the portion of the photosensitive resin layer exposed in step (2); in this order, to form a metal pillar pattern having an aspect ratio of 2.7 or more.

11. A photosensitive resin laminate is laminated onto a copper substrate, and exposed using a projection exposure machine equipped with a lens having a numerical aperture (NA) of 0.16 or less, with 1% by mass of Na used as the developer. ２ CO ３ A photosensitive resin laminate used to form circular holes with an aspect ratio of 3.0 or more by a development process using an aqueous solution for a development time of 2.5 times or more the minimum development time, characterized in that the photosensitive resin layer in the photosensitive resin laminate has a film thickness of 100 μm or more, and further contains an alkali-soluble polymer component containing a monomer having an aromatic ring as a copolymer component.

12. The photosensitive resin laminate according to claim 11, wherein the development speed of the photosensitive resin layer is 0.25 μm / s or more and 3.00 μm / s or less.

13. The photosensitive resin laminate according to claim 11, wherein the ratio A / T of the absorbance (A) at 365 nm to the film thickness (T) [μm] of the photosensitive resin layer is 0.003 or less.

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