WO2026023645A1 - Stratifié de résine photosensible - Google Patents

Stratifié de résine photosensible

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Publication number
WO2026023645A1
WO2026023645A1 PCT/JP2025/026117 JP2025026117W WO2026023645A1 WO 2026023645 A1 WO2026023645 A1 WO 2026023645A1 JP 2025026117 W JP2025026117 W JP 2025026117W WO 2026023645 A1 WO2026023645 A1 WO 2026023645A1
Authority
WO
WIPO (PCT)
Prior art keywords
photosensitive resin
mass
compound
forming
resist pattern
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/026117
Other languages
English (en)
Japanese (ja)
Inventor
創 古谷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Kasei Corp, Asahi Chemical Industry Co Ltd filed Critical Asahi Kasei Corp
Publication of WO2026023645A1 publication Critical patent/WO2026023645A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
    • C08F267/06—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • This disclosure relates to a photosensitive resin laminate.
  • photolithography Traditionally, the manufacture of printed wiring boards and precision metal processing have been achieved using photolithography.
  • the photosensitive resin laminates used in photolithography are classified into negative-type, in which unexposed areas are dissolved and removed, and positive-type, in which exposed areas are dissolved and removed.
  • the protective layer is peeled off from the photosensitive resin laminate.
  • the photosensitive resin layer and support are laminated onto a substrate such as a copper-clad laminate or a copper-sputtered thin film in the order of substrate, photosensitive resin layer, and support.
  • the photosensitive resin layer is exposed to light through a photomask bearing the desired wiring pattern.
  • the support is peeled off from the laminate, and the unexposed or exposed areas are dissolved or dispersed and removed using a developer, forming a resist pattern on the substrate.
  • the substrate bearing the resist pattern can then be subjected to plating processes such as copper plating or solder plating, and the resist pattern can then be peeled off to form metal patterns, wiring, metal pillars or semiconductor bumps, semiconductor packaging, and more.
  • 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.
  • Patent Document 2 also investigates the relationship between the film thickness and absorbance of the photosensitive resin layer.
  • plating is becoming increasingly popular as a method for forming metal wiring.
  • the shape of the wiring formed using plating depends on the shape and thickness of the resist pattern.
  • Plating generally uses a photosensitive resin laminate with a thick photosensitive resin layer, and the resist pattern formed by exposing and developing the photosensitive resin laminate is subjected to metal plating and then treated with a stripping solution.
  • the strippability of the cured resist pattern is poor, the solubility of the stripped pieces will also be poor, and the stripping process, which involves immersing the resist pattern in the stripping solution, stripping, and dissolution, will take a long time, and the stripped cured resist may not dissolve completely and remain in the stripping solution as residue.
  • stripper solution fatigue For example, if a photosensitive resin with poor processability in a stripper solution is used, the stripped hardened resist will not dissolve and will remain as a residue in the stripper solution. The retained stripping residue will remain on the plating pattern, causing defects. For this reason, the processability of the photosensitive resin in a stripper solution (hereinafter also referred to as "strip processability") is required. Furthermore, the stripper solution used to remove the cured resist pattern consumes its components as it is removed. If a photosensitive resin that consumes components significantly is used, problems such as stripping residue will easily occur, reducing productivity, unless the stripper solution is made up more frequently. For this reason, it is necessary to reduce the frequency of stripper solution make-up (hereinafter also referred to as “stripper solution fatigue").
  • plating sinking a phenomenon whereby plating sinks into the bottom of the hardened resist pattern during plating processing (hereinafter referred to as "plating sinking"), which causes the metal pattern to trail off the bottom.
  • an object of the present disclosure is to provide a photosensitive resin laminate that can improve the releasability of a resist pattern.
  • the present inventors have discovered that the above-mentioned problems can be solved by specifying the structure and content of each component of a photosensitive resin composition in a photosensitive resin laminate including a support film and a photosensitive resin layer containing a photosensitive resin composition, and have completed the present invention.
  • Examples of embodiments of the present disclosure are listed in the following items.
  • a photosensitive resin laminate for forming a resist pattern for forming a metal pillar and a semiconductor bump comprising a support film and a photosensitive resin layer containing a photosensitive resin composition
  • the photosensitive resin composition contains, relative to the total solid content of the photosensitive resin composition, (A) 30% by mass to 70% by mass of an alkali-soluble polymer; (B) 20% by mass to 50% by mass of a compound having an ethylenically unsaturated bond; and (C) 0.01% by mass to 20% by mass of a photopolymerization initiator; Including,
  • the component (B) is at least (B-1) a compound having a cyclic group, an ethylene oxide chain, and two acryloyl groups in one molecule; and (B-2) a compound having three or more acryloyl groups; and wherein the photosensitive resin layer has a thickness of 80 ⁇ m or more.
  • the compound (B-1) is represented by the following general formula (II): ⁇ wherein each EO independently represents ethylene oxide, each A independently represents an acryloyl group, and each m and n independently represents an integer of 1 to 100 ⁇ 2.
  • the photosensitive resin laminate for forming a resist pattern for forming metal pillars and semiconductor bumps according to any one of items 1 to 6, wherein the mass ratio of the propylene oxide or butylene oxide-modified monomer to the ethylene oxide-modified monomer in the component (B) ((propylene oxide-modified monomer + butylene oxide-modified monomer)/ethylene oxide-modified monomer) is 0 or more and less than 0.1.
  • a photosensitive resin laminate for forming a resist pattern to form a metal pillar and a semiconductor bump comprising a support film and a photosensitive resin layer containing a photosensitive resin composition
  • the photosensitive resin composition contains, relative to the total solid content of the photosensitive resin composition, (A) 30% by mass to 70% by mass of an alkali-soluble polymer; (B) 20% by mass to 50% by mass of a compound having an ethylenically unsaturated bond; and (C) 0.01% by mass to 20% by mass of a photopolymerization initiator;
  • the component (B) is at least (B-1) A compound having a cyclic group, an ethylene oxide chain, and two acryloyl groups in one molecule;
  • a photosensitive resin laminate for forming a resist pattern for forming a metal pillar and a semiconductor bump wherein in the component (B), a mass ratio (methacrylate monomer/acrylate monomer) of a compound having a methacryloyl group to
  • the compound (B-1) is represented by the following general formula (II): ⁇ wherein each EO independently represents ethylene oxide, each A independently represents an acryloyl group, and each m and n independently represents an integer of 1 to 100 ⁇ Item 12.
  • a photosensitive resin laminate that can improve the removability of resist patterns, thereby improving the solubility of peeled pieces of resist patterns even in thick photosensitive resin laminates, significantly shortening the stripping process time, and suppressing peeling residue or plating penetration.
  • 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, as necessary.
  • the photosensitive resin laminate of the present disclosure is also preferably used for forming a resist pattern for forming metal pillars and semiconductor bumps.
  • the photosensitive resin layer includes a photosensitive resin composition
  • the photosensitive resin composition includes, relative to the total solid content of the photosensitive resin composition, (A) 30% to 70% by mass of an alkali-soluble polymer, (B) 20% to 50% by mass of a compound having an ethylenically unsaturated bond, and (C) 0.01% to 20% by mass of a photopolymerization initiator.
  • the photosensitive resin layer may also include, relative to the total solid content of the photosensitive resin layer, (A) 30% to 70% by mass of an alkali-soluble polymer, (B) 20% to 50% by mass of a compound having an ethylenically unsaturated bond, and (C) 0.01% to 20% by mass of a photopolymerization initiator.
  • the photosensitive resin layer may optionally contain a polymer other than component (A), a monomer other than component (B), an initiator other than component (C), and other components such as dyes, antioxidants, plasticizers, etc.
  • a photosensitive resin laminate capable of improving the releasability of a resist pattern is specified by optimizing the thickness of the photosensitive resin layer, the structure and content of each component contained therein, for example, the structure and content of component (B) and/or component (A), etc.
  • component (B) may include at least two types of monomers: a bifunctional monomer and a tri- or higher functional polyfunctional monomer; or component (B) may not only include a bifunctional monomer but also specify the mass ratio (methacrylate monomer/acrylate monomer) of the compound having a methacryloyl group to the compound having an acryloyl group in component (B).
  • component (B) may include at least two types of monomers: a bifunctional monomer and a tri- or higher functional polyfunctional monomer; or component (B) may not only include a bifunctional monomer but also specify the mass ratio (methacrylate monomer/acrylate monomer) of the compound having a methacryloyl group to the compound having an acryloyl group in component (B).
  • the bifunctional monomer may be, for example, (B-1) a compound having a cyclic group, an ethylene oxide chain, and two acryloyl groups in one molecule.
  • the polyfunctional monomer may be, for example, (B-2) a compound having three or more acryloyl groups.
  • a photosensitive resin laminate can be provided that contains a bifunctional monomer as component (B), and in which the content or composition of components other than component (B) is specified.
  • the bifunctional monomer can include, for example, (B-1), a compound having a cyclic group, an ethylene oxide chain, and two acryloyl groups in one molecule, and the composition of component (A) and/or the combination of component (A) and component (B) can be specified, which can contribute to improving resist pattern strippability.
  • the photosensitive resin composition and photosensitive resin layer according to the present disclosure contain an alkali-soluble polymer.
  • the amount of the alkali-soluble polymer is 30% by mass to 70% by mass, preferably 40% by mass to 70% by mass, and more preferably 50% by mass to 70% by mass, based on the total solids mass of the photosensitive resin composition or the photosensitive resin layer.
  • an alkali-soluble polymer refers to a polymer that can be dissolved in an alkaline aqueous solution.
  • the alkali-soluble polymer preferably contains a copolymer in which a monomer having an aromatic ring is a copolymerization component.
  • Alkali-soluble polymers containing a monomer having an aromatic ring as a copolymerization component are hydrophobic and have a swelling-suppressing effect, resulting in excellent resist pattern resolution.
  • the mass ratio of units having an aromatic ring in the alkali-soluble polymer is preferably within the range of 50 to 90 mass%, more preferably 70 to 90 mass%, and even more preferably 75 to 85 mass%.
  • Examples of monomers having an aromatic ring include (meth)acrylates having an aromatic group; and aromatic vinyl compounds such as styrene and styrene derivatives.
  • (meth)acrylate means acrylate or methacrylate
  • (meth)acrylic means acrylic or methacrylic
  • (meth)acryloyl means acryloyl or methacryloyl.
  • styrene derivatives include oxystyrene, hydroxystyrene, acetoxystyrene, alkylstyrene, and halogenoalkylstyrene.
  • (meth)acrylates having an aromatic group are preferred from the viewpoint of the developability of the resist pattern.
  • 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, a benzyl group, a biphenyl group, and a naphthyl group.
  • the hydrogen atom of the aromatic group may be unsubstituted or substituted, and if substituted, examples of the substituent include a hydrocarbon group having 1 to 5 carbon atoms, a hydroxyl group, a halogen group, etc.
  • the alkali-soluble polymer preferably contains a copolymer with benzyl (meth)acrylate as a copolymerization component as a (meth)acrylate having an aromatic group.
  • aromatic rings are hydrophobic and therefore thought to have low developability, whereas benzyl (meth)acrylate is preferred because it has high flexibility and excellent developability.
  • the proportion of benzyl (meth)acrylate contained as a copolymerization component in the alkali-soluble polymer is 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 mass of all monomers constituting the alkali-soluble polymer.
  • a higher proportion of benzyl (meth)acrylate improves the stripping properties 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 mass of all monomers constituting the alkali-soluble polymer.
  • 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.
  • Acid equivalent refers to the mass in grams of alkali-soluble polymer per equivalent of carboxyl group.
  • An acid equivalent of 350 or more offers advantages such as a shorter minimum development time, improved resolution, reduced stripper fatigue, and prevention of resist wrinkling during storage.
  • There is no upper limit to the acid equivalent but it is preferably 600 or less, for example.
  • An acid equivalent of 600 or less can improve developability and strippability.
  • the lower limit of the proportion of acid groups is not particularly limited, but may be, for example, 0% by mass, greater than 0% by mass, or 1% by mass or more.
  • the weight-average molecular weight of the alkali-soluble polymer is 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 viewpoints of reducing development aggregates and improving the properties of the unexposed film in the photosensitive resin laminate, such as edge fuse properties and cut-chip properties.
  • Edge fuse properties are the property that prevents the photosensitive resin layer from protruding from the edge of the roll when the photosensitive resin laminate is wound into a roll.
  • Cut-chip properties are the property that prevents chips from flying off when the unexposed film is cut with a cutter. If the cut-chip properties are poor, scattered chips may adhere to, for example, the top surface of the photosensitive resin laminate, and these chips may be transferred to the mask in the subsequent exposure process, causing defects.
  • the alkali-soluble polymer may contain a copolymerization component other than a monomer having an aromatic ring.
  • copolymerization 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 half ester (meth)acrylic acid, alkyl (meth)acrylates; (meth)acrylonitrile; and (meth)acrylamide.
  • 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 solids mass of the alkali-soluble polymer.
  • the alkali-soluble polymer it is preferable for the alkali-soluble polymer to contain structural units derived from methacrylic acid, as this provides excellent developability and a good balance with resolution.
  • methacrylic acid is contained in the alkali-soluble polymer, the proportion 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 solids mass of the alkali-soluble polymer.
  • the mass proportion of structural units derived from methacrylic acid in the alkali-soluble polymer may be, for example, 0% by mass or greater.
  • the alkali-soluble polymer preferably contains structural units derived from acrylic acid, as this provides excellent flexibility for the cured film or cured resist pattern, and therefore excellent developability.
  • the mass ratio of the structural units derived from acrylic acid in the alkali-soluble polymer is preferably 20 mass% or less, more preferably 10 mass% or less, and even more preferably 5 mass% or less, based on the solids mass of the alkali-soluble polymer.
  • Alkali-soluble polymers that contain alkyl groups are preferred because they provide excellent flexibility in the cured film or cured resist pattern, and therefore excellent developability.
  • the mass ratio of structural units derived from alkyl group-containing monomers in the alkali-soluble polymer is preferably in the range of 1 to 20 mass%, and more preferably 1 to 10 mass%, based on the solids mass of the alkali-soluble polymer.
  • the alkali-soluble polymer preferably contains an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 4 to 10 carbon atoms, and even more preferably an alkyl group having 6 to 10 carbon atoms.
  • the alkyl group of the alkyl (meth)acrylate may be linear, branched, or cyclic, and may have, for example, 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and 12 or less, 11 or less, 10 or less, 9 or less, or 8 or less carbon atoms.
  • alkyl group of the alkyl (meth)acrylate examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, ethylhexyl, nonyl, decyl, undecyl, and dodecyl groups.
  • the 2-ethylhexyl group is even more preferred from the viewpoints of shortening development time and reducing footing of the resist pattern.
  • an alkali-soluble polymer containing 2-ethylhexyl acrylate as a copolymerization component can be obtained.
  • Preferred combinations of copolymerization components in alkali-soluble polymers include, for example, (meth)acrylic acid and benzyl (meth)acrylate; (meth)acrylic acid, benzyl (meth)acrylate and an aromatic vinyl compound; and (meth)acrylic acid, benzyl (meth)acrylate and an alkyl (meth)acrylate. More specific examples include methacrylic acid and benzyl methacrylate; acrylic acid, benzyl methacrylate and styrene; and acrylic acid, benzyl methacrylate and 2-ethylhexyl acrylate.
  • the photosensitive resin composition and photosensitive resin layer according to the present disclosure contain a compound having an ethylenically unsaturated bond.
  • the amount of the compound having an ethylenically unsaturated bond is 20% by mass to 50% by mass, preferably 20% by mass to 40% by mass, based on the total solids mass of the photosensitive resin composition or the photosensitive resin layer.
  • the ethylenically unsaturated bond can be polymerized by irradiation with light in the presence of a photopolymerization initiator, thereby curing the photosensitive resin layer.
  • the compound having an ethylenically unsaturated bond may have a 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.
  • a double bond equivalent of 150 or more tends to improve resistance to plating penetration and peelability.
  • the double bond equivalent of the compound having an ethylenically unsaturated bond may be, for example, 500 or less, 400 or less, or 300 or less.
  • double bond equivalent means the molecular weight per ethylenically unsaturated bond.
  • 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.
  • 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, swelling is suppressed, and resolution tends to be excellent.
  • the ethylenically unsaturated bonds in the photosensitive resin layer are preferably derived from at least ethylenically unsaturated methacryloyl or acryloyl groups.
  • 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.
  • concentration of ethylenically unsaturated bonds in the photosensitive resin layer refers to the total number of moles of ethylenically unsaturated groups per gram of the photosensitive resin layer.
  • a compound having an ethylenically unsaturated bond for example, a compound having a (meth)acryloyl group can be used. While not wishing to be bound by theory in this disclosure, it is believed that the mechanism by which a photosensitive resin laminate or a resist pattern dissolves in a stripping solution such as an aqueous tetraalkylammonium hydroxide solution is that the compound having an ethylenically unsaturated bond contained in the photosensitive resin layer hydrolyzes, causing the crosslinked portions of the photosensitive resin layer to dissolve in the stripping solution while decomposing.
  • a stripping solution such as an aqueous tetraalkylammonium hydroxide solution
  • compounds having an acryloyl group are preferred because they have better hydrolysis properties than compounds having a methacryloyl group (methacrylate monomers), making it easier for the acrylate monomer to dissolve and be stripped during the stripping process.
  • the mass ratio of the compound having a methacryloyl group to the compound having an acryloyl group (methacrylate monomer/acrylate monomer) 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. Because acrylate monomers are more hydrolyzable than methacrylate monomers and tend to decompose more easily in the stripper solution, it is preferable that the compound having an ethylenically unsaturated bond contains more acrylate monomers than methacrylate monomers. Furthermore, it is preferable that the compound having an ethylenically unsaturated bond does not contain methacrylate monomers, or that it contains them in a mass ratio less than half that of the acrylate monomers.
  • the ratio of methacrylate monomer in the compound having an ethylenically unsaturated bond is preferably less than 50% by mass, more preferably 30% by mass, even more preferably less than 20% by mass, still more preferably less than 10% by mass, 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.
  • alkylene oxides can be modified with alkylene oxides as desired, specifically, they can have one or more alkylene oxide chains in the molecule.
  • alkylene oxides include methylene oxide (MO), ethylene oxide (EO), propylene oxide (PO), trimethylene oxide, butylene oxide (BO), tetramethylene oxide, etc.
  • alkylene oxides As these alkylene oxides, ethylene oxide (EO), which has two carbon atoms, or alkylene oxides with three or more carbon atoms are likely to be used. As alkylene oxides with three or more carbon atoms, propylene oxide (PO) or butylene oxide (BO) are particularly likely to be 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.
  • ethylene oxide EO
  • propylene oxide PO
  • trimethylene oxide butylene oxide
  • BO butylene oxide
  • tetramethylene oxide raw material compounds thereof
  • the compound having an ethylenically unsaturated bond When a compound having an ethylenically unsaturated bond has a relatively hydrophilic side chain, the compound tends to have good solubility in a stripping solution containing a large amount of water or a hydrophilic solvent, so the alkylene oxide chain contained in the compound is preferably relatively hydrophilic. That is, as a compound (monomer) having an alkylene oxide-modified ethylenically unsaturated bond, an EO-modified monomer is preferable compared to a monomer modified with an alkylene oxide having 3 or more carbon atoms.
  • the mass ratio of the monomer modified with an alkylene oxide having 3 or more carbon atoms to the EO-modified monomer is preferably 0 or more and less than 0.1.
  • Monomers not having an alkylene oxide chain are counted as EO-modified monomers.
  • the mass ratio of the PO- or BO-modified monomer to the EO-modified monomer in the compound having an ethylenically unsaturated bond ((PO-modified monomer + BO-modified monomer)/EO-modified monomer) is preferably 0 or more and less than 0.1.
  • Monomers without an alkylene oxide chain are calculated as EO-modified monomers.
  • the ratio of the PO monomer and/or BO monomer in the compound having an ethylenically unsaturated bond is preferably 30% by mass or less, more preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 0% by mass, based on the total solids mass of the compound having an ethylenically unsaturated bond.
  • the number of moles of EO units in a compound having an ethylenically unsaturated bond is preferably within the range of 1 to 30, more preferably 4 to 20, and even more preferably 4 to 10 per mole of compound. Note that if the number of moles of EO units exceeds 1, the compound having an ethylenically unsaturated bond contains a repeating unit having an EO chain.
  • the number of functional groups in a compound having an ethylenically unsaturated bond tends to be higher as the number increases, while the number decreases as the number increases, resulting in better releasability. Therefore, the number of functional groups in a compound having an ethylenically unsaturated bond can be determined based on the balance between resolution and releasability.
  • the number of functional groups in a compound having an ethylenically unsaturated bond can be, for example, monofunctional (hereinafter also referred to as monofunctional), difunctional or more, trifunctional or more, tetrafunctional or more, pentafunctional or more, hexafunctional or more, trifunctional to 10functional, trifunctional to hexafunctional, or tetrafunctional to hexafunctional, or a combination of multiple compounds with different numbers of functional groups.
  • “functionality” refers to the number of ethylenically unsaturated bonds per molecule of a compound. For example, in the case of an acrylate monomer, it is defined as the number of acryloyl groups per molecule, and in the case of a methacrylate monomer, it is defined as the number of methacryloyl groups per molecule.
  • Compounds having a monofunctional ethylenic double bond are preferred because they have excellent solubility in the stripping solution.
  • Examples of compounds having a monofunctional ethylenic double bond include compounds in which (meth)acrylic acid is added to one end of a (poly)alkylene glycol; and compounds in which (meth)acrylic acid is added to one end of a (poly)alkylene glycol and a group without an ethylenic double bond, such as an alkyl group, is added to the other end.
  • the alkylene in the (poly)alkylene glycol is preferably an alkylene group having 2 to 10 carbon atoms, more preferably 2 to 4 carbon atoms, such as a 1,2-ethylene group, a 1,2-propylene group, or a butylene group.
  • the content of the monofunctional monomer in the compound having an ethylenic double bond is preferably 1 to 30 mass%, more preferably 1 to 20 mass%, and even more preferably 5 to 15 mass%, based on the total solids mass of the compound having an ethylenically unsaturated bond.
  • bifunctional or higher functional compounds include compounds having a skeleton such as (poly)alkylene glycol, bisphenol A, trimethylolpropane, glycerin, pentaerythritol, or dipentaerythritol, in which at least two or all of the hydrogen atoms in the hydroxyl groups are substituted with functional groups having an ethylenically unsaturated bond, preferably functional groups having a (meth)acryloyl group, and more preferably functional groups having an acryloyl group.
  • a skeleton such as (poly)alkylene glycol, bisphenol A, trimethylolpropane, glycerin, pentaerythritol, or dipentaerythritol, in which at least two or all of the hydrogen atoms in the hydroxyl groups are substituted with functional groups having an ethylenically unsaturated bond, preferably functional groups having a (meth)acryloyl group, and more preferably
  • the compound having a (poly)alkylene glycol skeleton and a bifunctional ethylenically unsaturated bond includes compounds represented by the following general formula (I): ⁇ wherein each Y independently represents an alkylene group, R 1 and R 2 independently represent a methyl group or a hydrogen atom, and each n independently represents an integer of 1 to 50. ⁇ Examples of the compound include compounds represented by the following formula:
  • each Y is independently an alkylene group preferably having 2 to 10 carbon atoms, more preferably 2 to 4 carbon atoms, such as a 1,2-ethylene group, a 1,2-propylene group, or a butylene group.
  • the (Y-O) portion may contain repeating units of different alkylene oxides, or may consist of repeating units of the same alkylene oxide. When the (Y-O) portion contains different alkylene oxides, the arrangement may be random, alternating, or block.
  • n represents an integer of 1 to 50, preferably 3 to 20, and more preferably 6 to 10.
  • examples of the compound represented by the general formula (I) include: Diacrylate of hexaethylene glycol, diacrylate of heptaethylene glycol, Diacrylate of octaethylene glycol, diacrylate of nonaethylene glycol, Decaethylene glycol diacrylate, Hexapropylene glycol diacrylate, Heptapropylene glycol diacrylate, Octapropylene glycol diacrylate, Examples include diacrylate of nonapropylene glycol and diacrylate of decapropylene glycol.
  • 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, from the viewpoints of resistance to plating penetration, stripper processability, and stripper fatigue resistance, and is optionally 500 or less, 400 or less, or 300 or less.
  • the bifunctional monomer is preferably a compound (B-1) having a cyclic group, an ethylene oxide (EO) chain, and two acryloyl groups in one molecule.
  • the photosensitive resin composition or photosensitive resin layer contains the compound (B-1)
  • it tends to have excellent developability, resolution, and stripper solubility.
  • the compound (B-1) has a cyclic group, it tends to have improved resistance to plating penetration.
  • the cyclic group may be single or multiple
  • the EO chain may be located on one or both sides of the cyclic group
  • the two acryloyl groups may be located in any positions.
  • the number of moles of the EO chains in the (B-1) compound is preferably within the range of 1 to 30, more preferably 4 to 20, and even more preferably 4 to 10.
  • An example of a (B-1) compound is a compound that has a hydrogenated bisphenol A skeleton, both sides of the hydrogenated bisphenol A skeleton are EO-modified, and both ends have acryloyl groups.
  • Hydrogenated bisphenol A is a compound in which hydrogen is added to the aromatic ring of bisphenol A.
  • the (B-1) compound is preferably a compound in which the cyclic group is an aromatic ring. That is, the (B-) compound is preferably a compound having an aromatic ring, an ethylene oxide (EO) chain, and two acryloyl groups in one molecule. When the cyclic group is an aromatic ring, resistance to plating penetration tends to be further improved. Examples of such compounds include compounds with a bisphenol A skeleton, in which both sides of the bisphenol A skeleton are EO-modified and which have acryloyl groups on both ends. The bisphenol A skeleton in the (B-1) compound not only improves the strength of the crosslinked film, but also improves resolution.
  • the compound having a bisphenol A skeleton, both ends of which are EO-modified, and both ends of which have acryloyl groups is preferably a diacrylate of ethylene oxide (EO)-modified bisphenol A.
  • the diacrylate of ethylene oxide-modified bisphenol A is preferably a diacrylate of ethylene oxide-modified bisphenol A represented by the following general formula (II): ⁇ wherein each EO independently represents ethylene oxide, each A independently represents an acryloyl group, and each m and n independently represents an integer of 1 to 100 ⁇
  • 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, from the viewpoint of improving the strippability of the resist pattern.
  • examples of the compound represented by the general formula (II) include: Diacrylate of polyethylene glycol in which an average of 1 mole of ethylene oxide is added to each end of bisphenol A, Diacrylate of polyethylene glycol in which an average of 2 moles of ethylene oxide are added to each end of bisphenol A, Diacrylate of polyethylene glycol in which an average of 3 moles of ethylene oxide are added to each end of bisphenol A, Diacrylate of polyethylene glycol in which an average of 4 moles of ethylene oxide are added to each end of bisphenol A, Diacrylate of polyethylene glycol in which an average of 5 moles of ethylene oxide are added to each end of bisphenol A, Diacrylate of polyethylene glycol in which an average of 6 to 9 moles of ethylene oxide are added to each end of bisphenol A, Diacrylate of polyethylene glycol in which an average of 10 moles of ethylene oxide are added to each end of bisphenol A, Diacrylate of polyethylene glycol in which an average of 11 to 19 moles of ethylene oxide are added to
  • 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, from the viewpoints of resistance to plating penetration, stripper processability, and stripper fatigue resistance, and is optionally 500 or less, 400 or less, or 300 or less.
  • the photosensitive resin composition or photosensitive resin layer preferably contains a trifunctional or higher polyfunctional monomer as a compound having an ethylenically unsaturated bond.
  • At least two types of monomers are preferred as the compound having an ethylenically unsaturated bond, and a combination of a bifunctional monomer and a trifunctional or higher polyfunctional monomer is more preferred.
  • a compound (B-2) having three or more acryloyl groups is preferred.
  • the photosensitive resin composition or photosensitive resin layer contains the (B-2) compound, it tends to have excellent developability, resolution, and stripper solubility.
  • the (B-2) compound for example, among the tri- or higher functional monomers described below, one having an acryloyl group as the group having an ethylenically unsaturated bond may be used.
  • Examples of compounds having a trimethylolpropane skeleton and a trifunctional ethylenically unsaturated bond include compounds represented by the following general formula (III): ⁇ wherein n 1 , n 2 and n 3 each independently represent an integer of 1 to 25, provided that n 1 + n 2 + n 3 is an integer of 3 to 75, and R 1 , R 2 and R 3 each independently represent a methyl group or a hydrogen atom. ⁇ Examples of the compound include compounds represented by the following formula:
  • n1 , n2 , and n3 are each independently an integer of 1 to 25, preferably 1 to 10, and more preferably 1 to 3.
  • n1 + n2 + n3 is an integer of 3 to 75, preferably 3 to 30, more preferably 3 to 15, and even more preferably 3 to 9.
  • n1 + n2 + n3 is 9 or greater, this is preferred from the viewpoints of suppressing the occurrence of a resist base, improving film strength, and imparting flexibility to the cured film.
  • n1 + n2 + n3 is 75 or less, this is preferred from the viewpoints of high resolution and adhesion, good release properties, and controlling edge fusing properties.
  • Specific examples of the compound represented by the general formula (III) include: a triacrylate in which an average of 3 moles of ethylene oxide in total have been added to the terminal hydroxyl groups of trimethylolpropane; a triacrylate in which an average of 9 moles of ethylene oxide in total have been added to the terminal hydroxyl groups of trimethylolpropane; a triacrylate in which an average of 15 moles of ethylene oxide in total has been added to the terminal hydroxyl groups of trimethylolpropane, and a triacrylate in which an average of 30 moles of ethylene oxide in total has been added to the terminal hydroxyl groups of trimethylolpropane; Examples include:
  • 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, from the viewpoints of resistance to plating penetration, stripper processability, and stripper fatigue resistance, and is optionally 500 or less, 400 or less, or 300 or less.
  • Examples of compounds having a glycerin skeleton and a trifunctional ethylenically unsaturated bond include compounds represented by the following formula (IV): ⁇ wherein each Y independently represents an alkylene group, each R independently represents a methyl group or a hydrogen atom, and each n independently represents an integer of 0 to 200 ⁇ Examples of the compound include compounds represented by the following formula:
  • each Y is independently an alkylene group preferably having 2 to 10 carbon atoms, more preferably 2 to 4 carbon atoms, such as a 1,2-ethylene group, a 1,2-propylene group, or a butylene group. From the standpoint of imparting flexibility to the cured film, improving film strength, suppressing development aggregation, and increasing the reactivity of the ethylenically unsaturated bonds, it is preferable that at least one or all of the Ys be a 1,2-ethylene group.
  • the (Y-O) moiety may contain repeating units of different alkylene oxides, or may consist of repeating units of the same alkylene oxide.
  • n is independently an integer from 0 to 200. It is preferable that at least one n is an integer from 1 to 200, and it is more preferable that three n's are integers from 1 to 200.
  • n may be 0, i.e., no alkylene oxide moiety may be present.
  • a total of n's of 1 or greater is preferred from the viewpoints of suppressing the occurrence of resist tails, improving film strength, and imparting flexibility to the cured film.
  • a total of n's of 200 or less is preferred from the viewpoints of high resolution and adhesion, good release properties, and controlling edge fusing properties.
  • 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, from the viewpoints of resistance to plating penetration, stripper processability, and stripper fatigue resistance, and is optionally 500 or less, 400 or less, or 300 or less.
  • Examples of compounds having a pentaerythritol skeleton and a tetrafunctional ethylenically unsaturated bond include compounds represented by the following general formula (V): ⁇ In the formula, n 1 , n 2 , n 3 and n 4 each independently represent an integer of 1 to 25, n 1 + n 2 + n 3 + n 4 is an integer of 4 to 100, R 1 , R 2 , R 3 and R 4 each independently represent a methyl group or a hydrogen atom, R 5 , R 6 , R 7 and R 8 each independently represent an alkylene group, and when there are multiple R 5 , R 6 , R 7 and R 8 , the multiple R 5 , R 6 , R 7 and R 8 may be the same or different.
  • Examples of the compound include compounds represented by the following formula:
  • R 5 , R 6 , R 7 , and R 8 are each independently an alkylene group preferably having 2 to 10 carbon atoms, more preferably 2 to 4 carbon atoms, such as a 1,2-ethylene group, a 1,2-propylene group, or a butylene group. From the viewpoints of imparting flexibility to the cured film, improving film strength, suppressing development aggregation, and increasing the reactivity of the ethylenically unsaturated bonds, it is preferred that at least one or all of R 5 , R 6 , R 7 , and R 8 be a 1,2-ethylene group.
  • n 1 +n 2 +n 3 +n 4 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. It is preferred that n 1 +n 2 +n 3 +n 4 is 4 or greater, from the viewpoints of suppressing the formation of a resist skirt, improving film strength, and imparting flexibility to the cured film. It is preferable that n 1 +n 2 +n 3 +n 4 is 100 or less from the viewpoints of high resolution and adhesion, good peeling properties, and controlling edge fusing properties.
  • Specific examples of the compound represented by the general formula (V) include: a tetraacrylate in which an average of 4 moles of ethylene oxide in total have been added to the terminal hydroxyl groups of pentaerythritol; tetraacrylate in which an average of 9 moles of ethylene oxide in total have been added to the terminal hydroxyl groups of pentaerythritol; a tetraacrylate in which an average of 12 moles of ethylene oxide in total have been added to the terminal hydroxyl groups of pentaerythritol; a tetraacrylate in which an average of 15 moles of ethylene oxide in total have been added to the terminal hydroxyl groups of pentaerythritol; a tetraacrylate in which an average of 20 moles of ethylene oxide in total have been added to the terminal hydroxyl groups of pentaerythritol; Examples include a tetraacrylate in which an average of 28 moles of ethylene oxide in total has been
  • 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, from the viewpoints of resistance to plating penetration, stripper processability, and stripper fatigue resistance, and is optionally 500 or less, 400 or less, or 300 or less.
  • the compound (B-2) is a compound represented by the following general formula (V1): ⁇ wherein each EO independently represents ethylene oxide, each A independently represents an acryloyl group, and k, l, m, and n independently represent an integer of 1 to 100 ⁇
  • the compound represented by general formula (V1) is preferred.
  • the compound represented by general formula (V1) can improve the crosslinking density, which in turn contributes to good resolution.
  • k, l, m, and n in general formula (V1) 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.
  • Examples of the compound having a dipentaerythritol skeleton and a hexafunctional ethylenically unsaturated bond include compounds represented by the following general formula (VI): ⁇ wherein each R independently represents a methyl group or a hydrogen atom, and each n independently represents an integer of 0 to 30 ⁇ In general formula (VI), n may be 0, that is, the alkylene oxide moiety may not be present.
  • each n is independently an integer from 0 to 30, preferably from 1 to 20, more preferably from 2 to 10, and even more preferably from 3 to 5.
  • the total of n is from 0 to 180, preferably from 6 to 120, more preferably from 12 to 60, and even more preferably from 18 to 30.
  • a total of n of 1 or more is preferred from the viewpoints of suppressing the occurrence of resist tails, improving film strength, and imparting flexibility to the cured film.
  • a total of n of 180 or less is preferred from the viewpoints of high resolution and adhesion, good release properties, and controlling edge fusing properties.
  • hexaacrylate compound represented by general formula (VI) include: Dipentaerythritol hexaacrylate, hexaacrylate in which a total of 1 to 36 moles of ethylene oxide are added to the six terminals of dipentaerythritol; hexaacrylate in which a total of 6 to 30 moles of ethylene oxide are added to the six terminals of dipentaerythritol; Hexaacrylate in which a total of 12 to 30 moles of ethylene oxide are added to the six terminals of dipentaerythritol, Examples include hexaacrylate in which a total of 18 to 30 moles of ethylene oxide are added to the six terminals of dipentaerythritol, and hexaacrylate in which a total of 1 to 10 moles of ⁇ -caprolactone are added to the six terminals of dipentaerythritol.
  • 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, from the viewpoints of resistance to plating submersion, stripper treatment ability, and stripper fatigue resistance, and is optionally 500 or less, 400 or less, or 300 or less.
  • the mass ratio (A/B) of the alkali-soluble polymer to the compound having an ethylenically unsaturated bond is preferably within 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.
  • a photopolymerization initiator is a compound that can initiate polymerization of a compound having an ethylenically unsaturated bond by irradiating the compound with light in the presence of the compound.
  • the amount of photopolymerization initiator in the photosensitive resin composition and the photosensitive resin layer is 0.01% by mass to 20% by mass, preferably 0.3% by mass to 10% by mass, and more preferably 1% by mass to 5% by mass, based on the total solids mass of the photosensitive resin composition and the photosensitive resin layer, respectively.
  • the amount of photopolymerization initiator is 0.01% by mass or more, an exposed pattern with a sufficient residual film rate after development can be obtained.
  • the amount of photopolymerization initiator is 20% by mass or less, light can be sufficiently transmitted to the bottom of the resist, resulting in high resolution and suppressing development aggregation in the developer.
  • photopolymerization initiators examples include imidazole compounds, aromatic ketones, acridine compounds, and N-aryl- ⁇ -amino acid compounds.
  • One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.
  • Imidazole compounds tend to improve the plating penetration resistance and suppress footing of resist patterns.
  • imidazole compounds include imidazoles with aliphatic groups, such as methylimidazole, 2-ethyl-4-methylimidazole, 1-isobutyl-2-methylimidazole, 2-ethyl-4-methylimidazole, ethylimidazole, isopropylimidazole, 2,4-dimethylimidazole, undecylimidazole, and heptadecylimidazole; and imidazoles with aromatic groups, such as 1-benzyl-2-methylimidazole, phenylimidazole (e.g., 2-phenylimidazole), 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, triarylimidazole, and dimers thereof.
  • aliphatic groups such
  • imidazoles having an aromatic group are preferred, triarylimidazole (e.g., lophine) or a dimer thereof is more preferred, and triarylimidazole dimer is even more preferred.
  • triarylimidazole dimers examples 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.
  • 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,
  • Aromatic ketones are preferred from the perspective of improving sensitivity.
  • aromatic ketones include benzophenone, N,N'-tetramethyl-4,4'-dimethylaminobenzophenone (Michler's ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-bis(diethylamino)benzophenone, 2-benzyl-2-dimethylamino-1-(4-monophornophenyl)-butanone-1, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1. Of these, 4,4'-bis(diethylamino)benzophenone is preferred.
  • 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)acrid
  • Suitable acridines include 1,7-bis(9,9'-acridinyl)heptane, 9-(4-dimethylaminophenyl)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)a
  • N-aryl- ⁇ -amino acid compounds are preferred from the perspective of improving sensitivity.
  • Examples of N-aryl- ⁇ -amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.
  • 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-phenanthraquinone, 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; Coumarin compounds;
  • the content of the triarylimidazole dimer in the photosensitive resin composition is preferably 0.3% by mass to 10% by mass, and more preferably 1% by mass to 5% by mass, based on the total solids mass of the photosensitive resin composition or photosensitive resin layer.
  • 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.
  • the photosensitive resin composition and the photosensitive resin layer may each further contain a dye.
  • the dye may contain at least one selected from leuco dyes, fluoran dyes, and other coloring substances.
  • the exposed portions develop color, improving visibility.
  • an inspection machine or the like reads the alignment marker for exposure, the contrast between the exposed and unexposed portions is increased, making them easier to recognize.
  • Leuco dyes include tris(4-dimethylaminophenyl)methane [leuco crystal violet] and bis(4-dimethylaminophenyl)phenylmethane [leucomalachite green]. From the viewpoint of good contrast, leuco crystal violet is preferred as the leuco dye.
  • 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 solids mass of the photosensitive resin composition and the photosensitive resin layer, respectively.
  • the amount of the dye is 0.1% by mass or more, the contrast between exposed and unexposed areas tends to be improved.
  • the amount of the dye is 10% by mass or less, the storage stability of the photosensitive resin layer tends to be improved, and the occurrence of aggregates during development tends to be suppressed.
  • coloring substances include fuchsin, phthalocyanine green, auramine base, paramagienta, crystal violet, methyl orange, Nile Blue 2B, malachite green (manufactured by Hodogaya Chemical Co., Ltd., Eisen (registered trademark) MALACHITE GREEN), basic blue 7 (e.g., Eisen (registered trademark) Victoria Pure Blue BOH conc., etc.), basic blue 20, and diamond green (manufactured by Hodogaya Chemical Co., Ltd., Eisen (registered trademark) DIAMOND GREEN GH).
  • 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 mass of the photosensitive resin composition and the photosensitive resin layer, respectively. If the amount of coloring substance is 0.001% by mass or more, contrast will improve, and if it is 1% by mass or less, storage stability will tend to improve.
  • the photosensitive resin composition and the photosensitive resin layer may each further contain a halogen compound, and preferably contain a halogen compound in combination with the leuco dye.
  • the combination of a leuco dye and a halogen compound tends to improve adhesion and contrast.
  • 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.
  • tribromomethylphenylsulfone is preferred.
  • Halogen compounds such as tribromomethylphenylsulfone are highly effective when used in combination with acridine compounds as photopolymerization initiators, and are preferred from the standpoints of improving resolution, adhesion, sensitivity, contrast, tent film puncture resistance, suppressing resist footing, and etching resistance.
  • the photosensitive resin composition and the photosensitive resin layer may each further contain an antioxidant.
  • the antioxidant can improve the thermal stability and storage stability of the photosensitive resin layer.
  • the antioxidant is preferably at least one compound selected from the group consisting of dicarboxylic polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles.
  • 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.
  • 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.
  • a mixture of 4-carboxy-1,2,3-benzotriazole and 5-carboxy-1,2,3-benzotriazole is preferred, with the mixing ratio being preferably about 1:1 by mass.
  • the total content of the antioxidant is preferably 0.01% by mass to 3% by mass, and more preferably 0.05% by mass to 1% by mass, based on the total solids mass of the photosensitive resin composition or photosensitive resin layer. If the amount of antioxidant is 0.01% by mass or more, the storage stability of the photosensitive resin layer will be improved, and if it is 3% by mass or less, sensitivity will tend to be maintained and discoloration of the dye will tend to be suppressed.
  • the photosensitive resin composition or the photosensitive resin layer may contain a plasticizer as needed.
  • the plasticizer 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; phthalates such as diethyl phthalate; o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetylcitrate, tri-n-propyl acetylcitrate, tri-n-butyl acetylcitrate, and the like; propylene glycol in which propylene
  • 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 solids mass of the photosensitive resin composition and the photosensitive resin layer, respectively.
  • a plasticizer amount of 1% by mass or more suppresses delays in development time and imparts flexibility to the cured film, while an amount of plasticizer of 50% by mass or less tends to suppress insufficient curing and edge fuse.
  • the photosensitive resin layer can be formed by dissolving each component in a solvent, applying the solution to a support film, and then drying.
  • the photosensitive resin composition according to the present disclosure may optionally contain a solvent in addition to the above-described components.
  • the resulting photosensitive resin layer may also contain residual solvent.
  • solvents include ketones such as methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropanol.
  • the film thickness of the photosensitive resin layer is 80 ⁇ m or more, preferably greater than 80 ⁇ m, more preferably 90 ⁇ m or more, even more preferably 100 ⁇ m or more, even more preferably 110 ⁇ m or more, and particularly preferably 115 ⁇ m or more.
  • photosensitive resin laminates having thick (80 ⁇ m or more) photosensitive resin layers are sometimes used.
  • a thick photosensitive resin layer can suppress the generation of laminar air, resulting in a photosensitive resin laminate suitable for plating processes, such as forming metal pillars.
  • the film thickness of the photosensitive resin layer may be 200 ⁇ m or more, 300 ⁇ m or more, or even 400 ⁇ m or more.
  • the upper limit of the film thickness of the photosensitive resin layer is not limited, but can be, for example, 1000 ⁇ m or less, 800 ⁇ m or less, or 500 ⁇ m or less.
  • the ratio (A) / (T) of the absorbance (A) of the photosensitive resin layer at a wavelength of 365 nm to the film thickness (T) of the photosensitive resin layer is preferably 0.02 or less, more preferably 0.01 or less, even more preferably 0.005 or less, and most preferably 0.003 or less.
  • the support film is preferably transparent and transmits light emitted from the exposure light source.
  • the support film 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 stretched as needed.
  • the haze of the support film is preferably 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 economy, but considering the function of maintaining strength, a thickness of 10 ⁇ m or more is preferred.
  • the support film is thick from the viewpoint of film thickness stability during coating, i.e., the thickness of the support film is preferably 20 ⁇ m or more, more preferably 50 ⁇ m or more, even more preferably 75 ⁇ m or more, and most preferably 100 ⁇ m or more.
  • the thickness of the support film may be 500 ⁇ m or less from the viewpoint of slit processability.
  • the thickness of the support film may be 10% or more, or 20% or more, of the thickness of the photosensitive resin layer.
  • the photosensitive resin laminate may have a protective layer on the surface of the photosensitive resin layer opposite the support film.
  • the protective layer serves to protect the photosensitive resin layer.
  • the protective layer preferably has an appropriate adhesive strength to the photosensitive resin layer. That is, it is preferable that the adhesive strength of the protective layer to the photosensitive resin layer is sufficiently smaller than the adhesive strength of the support film to the photosensitive resin layer, so that the protective layer can be easily peeled from the photosensitive resin laminate.
  • the protective layer for example, a polyethylene film, a polypropylene film, or a film with excellent peelability as disclosed in JP-A-59-202457 can be used.
  • the thickness of the protective layer is preferably 10 ⁇ m to 100 ⁇ m, more preferably 10 to 50 ⁇ m.
  • a photosensitive resin laminate can be produced by sequentially laminating a photosensitive resin layer and, if necessary, a protective layer on a support film.
  • Known lamination methods can be used.
  • the components used in the photosensitive resin layer are mixed with a solvent that dissolves them to obtain a uniform solution (coating liquid).
  • solvents include ketones such as methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropanol.
  • the amount of solvent is preferably such that the viscosity of the coating liquid is 500 to 4,000 mPa ⁇ s at 25°C.
  • the coating liquid can be applied to a support film and then dried to form a photosensitive resin layer on the support film.
  • Known methods can be used for coating, such as a method using a bar coater or roll coater.
  • a protective layer can be laminated on the photosensitive resin layer to produce a photosensitive resin laminate.
  • a resist pattern can be formed using the photosensitive resin laminate of the present disclosure.
  • a method for forming a resist pattern includes: a step of laminating a photosensitive resin layer of the photosensitive resin laminate on a substrate (laminating step); a step of exposing the laminated photosensitive resin laminate to light (exposure step); a step of developing the exposed photosensitive resin laminate to form a resist pattern (developing step); If desired, the method may include a step of heating the resulting resist pattern (heating step).
  • a metal pillar or a semiconductor bump can be formed using the substrate on which the resist pattern has been formed.
  • the method for forming the metal pillar or the semiconductor bump includes the following steps: Optionally, a descum and plating pretreatment 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); If desired, a step of etching the substrate on which the resist pattern has been formed (etching step); If desired, the method may include a step of peeling the resist pattern from the substrate (peeling step).
  • the laminate is adhered to a substrate such as a sputtered copper thin film using, for example, a hot roll laminator.
  • the sputtered copper thin film is preferably a copper-sputtered silicon wafer in which a copper layer is formed on a silicon wafer using a sputtering device.
  • the exposure step may be, for example: a step of exposing the photosensitive resin layer of the photosensitive resin laminate laminated on the substrate to light through a mask film having a desired wiring pattern in a state where the mask film is in close contact with the photosensitive resin layer; This may be a step of exposing a desired wiring pattern by a direct imaging exposure method, or a step of exposing by an exposure method in which an image of a photomask is projected through a lens.
  • the support film on the photosensitive resin layer is peeled off, and the unexposed areas (in the case of a negative type) or the exposed areas (in the case of a positive type) are developed and removed using an alkaline aqueous solution developer to form a resist pattern on the substrate.
  • an alkaline aqueous solution an aqueous solution of Na 2 CO 3 or K 2 CO 3 can be used.
  • the alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, but it is preferable to use an aqueous Na 2 CO 3 solution with a concentration of about 0.2 to 2% by mass and at a temperature of about 20 to 40°C.
  • the conditions for the exposure process and/or development process may be determined depending on the desired shape of the metal pillar or semiconductor bump.
  • the exposure process and/or development process may be carried out so as to form a hole-shaped resist pattern in which the ratio of circular hole diameter to film thickness is relatively high, exceeding 100 ⁇ m.
  • the circular hole diameter may be considered as the diameter of a circle inscribed in the polygon when the pattern is viewed from above.
  • the formed resist pattern may be further heated, for example, at about 50°C to 300°C for 1 minute to 5 hours.
  • a hot plate, hot air, infrared, or far-infrared heating furnace can be used for heating.
  • the substrate on which the resist pattern has been formed can be subjected to a plasma treatment and/or a water immersion treatment to carry out descum and plating pretreatment.
  • the substrate surface exposed by development e.g., the copper surface of a sputtered copper thin film
  • the plating solution is preferably a copper sulfate plating solution.
  • an etching solution may be sprayed onto the resist pattern formed through the above steps to etch the copper surface not covered by the resist pattern, thereby forming a circuit pattern.
  • the etching method include acid etching and alkaline etching, and the etching is carried out by a method suitable for the photosensitive resin laminate used.
  • aqueous solution having a stronger alkalinity than the developer is then treated with an aqueous solution having a stronger alkalinity than the developer, allowing the resist pattern to be stripped from the substrate.
  • stripping solutions include aqueous solutions of alkaline components with a concentration of about 2 to 5% by mass and a temperature of about 40 to 70°C; aqueous solutions of NaOH or KOH; dimethyl sulfoxide (DMSO); tetramethylammonium hydroxide (TMAH); mixtures of DMSO and TMAH; SPR920 (product name); R-101 (product name); and stripping solutions that do not contain DMSO (hereinafter referred to as "DMSO-free stripping solutions").
  • DMSO-free stripping solutions are preferred from the viewpoint of the effects of the photosensitive resin laminate according to the present disclosure and from the viewpoint of reducing the environmental impact.
  • the DMSO-free stripping solution may contain one or more of the above-mentioned components other than DMSO.
  • the photosensitive resin laminate, resist pattern, metal pillar, and semiconductor bump described above can be used, for example, to form semiconductor packages and wafer-level packages (WLPs).
  • WLPs wafer-level packages
  • Examples 1 to 43 and Comparative Example 1 ⁇ Preparation of Photosensitive Resin Laminate>
  • the materials shown in Tables 1 and 2 were mixed in the composition shown in Table 3 (where the number for each component indicates the amount (parts by mass) of solids), and methyl ethyl ketone measured so as to give a solids concentration of 60% was added, followed by thorough stirring and mixing to obtain a photosensitive resin coating solution.
  • the obtained coating solution was uniformly applied using a bar coater to the surface of a 16 ⁇ m thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., FB-40) used as a support film, and dried in a dryer at 95°C for 12 minutes to form a photosensitive resin layer.
  • the thickness (T) of the photosensitive resin layer after drying was 120 ⁇ m.
  • a 19 ⁇ m thick polyethylene film (GF-18, manufactured by Tamapoly Co., Ltd.) was laminated as a protective layer on the surface of the photosensitive resin layer that was not laminated with the support film, to obtain a photosensitive resin laminate.
  • ⁇ Evaluation board> As a substrate, a 6-inch silicon wafer (copper-sputtered silicon wafer) was prepared by forming a copper layer of 2000 angstroms ( ⁇ ) thick on the silicon wafer using a sputtering apparatus (L-440S-FHL) manufactured by Canon Anelva Corporation.
  • L-440S-FHL sputtering apparatus
  • a glass chrome mask was prepared in which a square lattice pattern of circular holes (a pattern in which the outer circles are exposed to light and the inner circles are not exposed to light for the photosensitive material) was arranged in diameters ranging from 10 ⁇ m to 100 ⁇ m in 5 ⁇ m increments, with a diameter:center spacing of 1:2.
  • a photosensitive resin layer was exposed at 200 mJ/ cm2 using an Ultratech Prisma ghi stepper (manufactured by Ultratech). The illuminance measured on the substrate surface was 2400 mW/ cm2 .
  • the PET film was peeled off from the substrate after the above-mentioned ⁇ exposure>, and then a 1 mass % Na 2 CO 3 aqueous solution was sprayed onto the photosensitive resin layer using a spin developer (Takizawa Sangyo Co., Ltd. spin developer AD-1200) at a liquid temperature of 30°C and a flow rate of 200 mL/min (spray development).
  • a spin developer Teakizawa Sangyo Co., Ltd. spin developer AD-1200
  • the minimum development time under the above conditions was determined in advance, and twice the respective minimum development time was set as the development time.
  • the “minimum development time” refers to the shortest time required for the photosensitive resin layer to completely dissolve when a wafer having a fully unexposed photosensitive resin layer laminated thereon is developed under the above-mentioned conditions. The smaller the “minimum development time” value, the better the performance.
  • the evaluation criteria for the minimum development time under these evaluation conditions are as follows: 160 seconds or less: Pass 140 seconds or less: Good 120 seconds or less: Very good 110 seconds or less: Best After development, water was sprayed onto the photosensitive resin layer (water washing spray). The conditions and time for the water washing spray were set the same as those for the developing spray.
  • the resist pattern of the substrate was subjected to plasma treatment (descum treatment and plating pretreatment) using a low-pressure plasma device (EXAM, manufactured by Shinko Seiki Co., Ltd.) under conditions of 50 Pa, 133 W, O 2 40 mL/min, CF 4 1 mL/min, and 1500 sec.
  • EXAM low-pressure plasma device
  • a copper sulfate plating solution was obtained by mixing 968 mL of SC-50 MU MA (manufactured by MICROFAB®), 20 mL of SC-50 R1 (manufactured by MICROFAB®), and 12 mL of SC-50 R2 (manufactured by MICROFAB®).
  • the resulting copper sulfate plating solution was used to copper-plate the substrate (6 cm x 12.5 cm) that had undergone the descum treatment and plating pretreatment described above using a Haring Cell Uniform Plating Apparatus (manufactured by Yamamoto Plating Tester Co., Ltd.).
  • the current value was adjusted so that copper was deposited at a height (thickness) of 1 ⁇ m per minute. This resulted in a 100 ⁇ m copper plating film.
  • the evaluation criteria for the minimum peeled piece dissolution time under these evaluation conditions are as follows: 500 seconds or less: Pass 350 seconds or less: Good 300 seconds or less: Very good 250 seconds or less: Best
  • the substrates immersed for the desired time were rinsed with water and air-dried. This resulted in the resist pattern being peeled off, yielding a substrate with a copper pillar pattern formed on it.
  • the copper plating film remaining after the above peeling functioned as copper pillars for wiring.
  • ⁇ Plating formability> The copper pillar pattern formed after the above-mentioned copper sulfate plating and peeling, each having a diameter of 60 ⁇ m and a center-to-center spacing of 120 ⁇ m between adjacent circular holes, was observed at 5x magnification using an optical microscope. 2,000 patterns were observed within an area of 1 cm x 3 mm, and the number of plating defects was counted as the number of areas where copper pillars were not formed or where there was unpeeled resist residue, and the plating formability was evaluated. The smaller the number of plating defects, the better the plating formability.
  • the evaluation criteria for the number of plating defects under these evaluation conditions are as follows. 5 or less: Pass 1 or less: Good 0: Best Note that in Comparative Example 1, the peeled pieces did not dissolve and the resist remained on the substrate after peeling, so it was not possible to evaluate plating formability.
  • ⁇ Plating penetration resistance> The copper pillar pattern formed after the above-mentioned ⁇ copper sulfate plating> and ⁇ peeling>, each having a diameter of 60 ⁇ m and a center-to-center spacing of 120 ⁇ m between adjacent circular holes, was observed at the bottom of the copper pillar at a magnification of 3000 times using a scanning electron microscope (S-3400N, manufactured by Hitachi High-Technologies Corporation) to check for the presence or absence of plating penetration. The absence of plating penetration indicates good performance.
  • the substrate was immersed for 10 minutes in a stripping solution consisting of 2% by weight of tetramethylammonium hydroxide, 8% by weight of propylene glycol, and 90% by weight of N-methylpyrrolidone.
  • the immersed substrate was rinsed with water and air-dried.
  • plating formability was evaluated by counting the number of plating defects as areas where copper pillars were not formed or where there was unstripped resist residue. A smaller number of plating defects indicates better plating formability.
  • the evaluation criteria for the number of plating defects under these evaluation conditions are as follows: 5 or less: Pass 1 or less: Good 0: Best

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Abstract

La présente invention concerne un stratifié de résine photosensible destiné à former un motif de réserve servant à former un pilier métallique et une bosse semi-conductrice, le stratifié de résine photosensible comprenant un film de support et une couche de résine photosensible qui contient une composition de résine photosensible. La composition de résine photosensible contient, par rapport à la teneur totale en solides de la composition de résine photosensible, (A) de 30 % en masse à 70 % en masse d'un polymère soluble dans les alcalis, (B) de 20 % en masse à 50 % en masse d'un composé qui a une liaison éthyléniquement insaturée, et (C) de 0,01 % en masse à 20 % en masse d'un initiateur de photopolymérisation. Le composant (B) comprend (B-1) un composé qui a un groupe cyclique, une chaîne d'oxyde d'éthylène, et deux groupes acryloyle dans chaque molécule, et (B-2) un composé qui a au moins trois groupes acryloyle. La couche de résine photosensible présente une épaisseur supérieure ou égale à 80 μm.
PCT/JP2025/026117 2024-07-25 2025-07-23 Stratifié de résine photosensible Pending WO2026023645A1 (fr)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011185962A (ja) * 2010-03-04 2011-09-22 Asahi Kasei E-Materials Corp 光重合性樹脂組成物積層体

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011185962A (ja) * 2010-03-04 2011-09-22 Asahi Kasei E-Materials Corp 光重合性樹脂組成物積層体

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