Classifications

• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
• • 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
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • 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
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
• • 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
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
  • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
• • 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
• • 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
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
• • 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
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/031—Organic compounds not covered by group G03F7/029
• • 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
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
• • 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
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • 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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • 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
  • G03F7/20—Exposure; Apparatus therefor
• • 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
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/40—Treatment after imagewise removal, e.g. baking
• • 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
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/42—Stripping or agents therefor
• • 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
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
  • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
• • 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
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
  • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material

Definitions

• the present invention relates to a photosensitive resin composition and the like.
• printed wiring boards are generally manufactured by a photolithography method.
• the photolithography method first, pattern exposure is performed on the photosensitive resin composition layer laminated on the substrate.
• the exposed portion of the photosensitive resin composition is polymerized and cured (in the case of a negative type) or solubilized in a developer (in the case of a positive type).
• the unexposed portion (in the case of negative type) or the exposed portion (in the case of positive type) is removed with a developer to form a resist pattern on the substrate.
• the resist pattern is peeled off from the substrate. Through these steps, a conductor pattern is formed on the substrate.
• a photosensitive resin composition is applied onto a substrate
• a solution of the photosensitive resin composition is applied to the substrate and dried, or a support or a layer comprising the photosensitive resin composition (Hereinafter also referred to as “photosensitive resin layer”)
• a method of laminating a photosensitive resin laminate (hereinafter also referred to as “dry film resist”) obtained by sequentially laminating a protective layer, if desired, on a substrate. Either is used. The latter is frequently used in the production of printed wiring boards.
• Patent Document 1 A photosensitive resin composition containing a (meth) acrylate compound having a skeleton derived from dipentaerythritol and a pyrazoline compound as a photosensitizer has been proposed (Patent Document 1).
• Patent Document 2 a (meth) acrylate compound having a skeleton derived from dipentaerythritol, a bisphenol A skeleton, and A photosensitive resin composition containing a di (meth) acrylate compound having an alkylene oxide chain has also been proposed (Patent Document 2).
• the resist pattern and the substrate may be washed with a chemical solution such as a degreasing solution. In comparison between before and after contact with the chemical, it is required that the change in the resist pattern shape is suppressed.
• Patent Documents 3 to 6 Furthermore, various photosensitive resin compositions have been proposed in order to improve resist characteristics (Patent Documents 3 to 6).
• Patent Document 3 a photosensitive resin composition containing pentaerythritol polyalkoxytetramethacrylate is studied as a compound having an ethylenically unsaturated bond from the viewpoint of the resist pattern sword shape, resolution, and residual film ratio.
• Patent Document 4 from the viewpoints of the resist pattern sedge shape, resolution, adhesion, minimum development time, and bleed-out property, as a monomer in the photosensitive resin composition, ethylene oxide-modified pentaerythritol tetra (meth) acrylate and A combination of di (meth) acrylate obtained by modifying bisphenol A with alkylene oxide and dipentaerythritol (meth) acrylate has been studied.
• Patent Documents 5 and 6 describe a photosensitive resin composition containing an alkali-soluble polymer having a glass transition temperature exceeding 106 ° C.
• the cured resist may have good flexibility so as to maintain adhesion to the substrate.
• the dry film resist may be wound and stored in a roll shape, but if the components of the dry film resist adhere to the support film surface by bleed out, stable wiring pattern production may be difficult. .
• JP 2012-048202 A International Publication No. 2015/012272 JP 2013-156369 A JP 2014-081440 A JP2013-117716A JP 2014-191318 A
• the present invention has been made with respect to the background art described above, and the problem to be solved by the present invention is a photosensitive resin that is excellent in at least one of adhesion, resolution, and storage stability. It is to provide a composition.
• a photosensitive resin composition comprising: A photosensitive resin layer comprising the photosensitive resin composition is formed on the substrate surface, and the resist pattern obtained by exposure and development is treated with a chemical solution for evaluating chemical resistance, and then the minimum line width of the cured resist line is obtained.
• the photosensitive resin composition whose is 17 micrometers or less.
• the photosensitive resin layer is formed on the surface of the substrate, exposed with a stove 41 step tablet as a mask, and then exposed at an exposure amount that the maximum remaining film stage number is 15 when developed.
• the exposure was performed In the FT-IR measurement, the peak height at a wave number of 810 cm ⁇ 1 before exposure is P, and the reaction rate of ethylenic double bonds in the compound (B) having an ethylenically unsaturated bond after the exposure is performed.
• Q The photosensitive resin composition according to [1], wherein a value of P ⁇ Q / R when the film thickness of the photosensitive resin layer is R is 0.21 or more.
• a photosensitive resin composition comprising: (A) The weight average value Tg total of the glass transition temperature Tg of the alkali-soluble polymer is 110 ° C. or less, and (B) three ethylenically unsaturated bonds as the compound having an ethylenically unsaturated bond.
• Tg total of the glass transition temperature Tg of the alkali-soluble polymer is 110 ° C. or less, and (B) three ethylenically unsaturated bonds as the compound having an ethylenically unsaturated bond
• the said photosensitive resin composition containing the (meth) acrylate compound which has the above.
• R 1 and R 2 each independently represent a hydrogen atom or a methyl group
• A is C 2 H 4
• B is C 3 H 6
• n 1 and n 3 are each independently N is an integer from 1 to 39
• n 1 + n 3 is an integer from 2 to 40
• n 2 and n 4 are each independently an integer from 0 to 29, and n 2 + n 4 is an integer from 0 to 30
• the arrangement of the repeating units of-(AO)-and-(BO)- may be random or block.
• (A) The weight average value Tgtotal of the glass transition temperature Tg of the alkali-soluble polymer is 105 ° C. or less
• (B) 70% by mass or more of the compound having an ethylenically unsaturated bond is a compound having a weight average molecular weight of 500 or more.
• the photosensitive resin composition as described in [8]. [19] (B1) The photosensitive resin composition according to [18], wherein the compound having at least three methacryloyl groups has a weight average molecular weight of 500 or more. [20] The photosensitivity according to [18] or [19], which includes (b2) a compound having a butylene oxide chain and one or two (meth) acryloyl groups as the compound (B) having an ethylenically unsaturated bond. Resin composition. [21] The photosensitive resin composition according to [20], wherein the compound (b2) having a butylene oxide chain and one or two (meth) acryloyl groups has a weight average molecular weight of 500 or more.
• a photosensitive resin composition excellent in at least one of adhesion, resolution and storage stability can be provided.
• the present embodiment a mode for carrying out the present invention (hereinafter abbreviated as “the present embodiment”) will be specifically described.
• the photosensitive resin composition contains (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator. If desired, the photosensitive resin composition may further contain other components such as (D) an additive.
• a photosensitive resin layer made of a photosensitive resin composition is formed on a substrate surface, and a resist pattern obtained by exposure and development is treated with a chemical solution for chemical resistance evaluation.
• the photosensitive resin composition is designed so that the minimum line width of the cured resist line is 17 ⁇ m or less.
• the minimum line width of the cured resist line is preferably 16 ⁇ m or less, more preferably 15 ⁇ m or less, still more preferably 12 ⁇ m or less, particularly preferably 10 ⁇ m or less, and most preferably 8 ⁇ m or less.
• the measurement method and conditions of the minimum line width of the cured resist line will be described in the chemical resistance evaluation of the examples.
• a weight average value Tg total of glass transition temperature Tg of the alkali-soluble polymer is 110 ° C. or lower
• a compound having an ethylenically unsaturated bond is ethylenic. It is the photosensitive resin composition containing the (meth) acrylate compound which has 3 or more of unsaturated bonds.
• the reaction rate can be improved, and the crosslinking density is increased.
• the unreacted component (B) hardly remains, and as a result, the photosensitive resin composition provides a resist pattern that is excellent in at least one of adhesion, resolution, and storage stability. It becomes a trend.
• a photosensitive resin layer composed of the photosensitive resin composition according to the present embodiment is formed on the substrate surface, exposed using a stove 41 step tablet as a mask, and then developed, the maximum number of remaining film steps is 15 steps.
• the photosensitive resin layer has the following formula: P ⁇ Q / R ⁇ 0.21 ⁇ In the formula, for the photosensitive resin layer, P represents a peak height at a wave number of 810 cm ⁇ 1 before exposure in FT-IR measurement, and Q represents (B) ethylene in a compound having an ethylenically unsaturated bond. Represents the reaction rate after exposure of the sexual double bond, and R represents the film thickness.
• the value represented by the formula P ⁇ Q / R described above is more preferably 0.22 or more, 0.23 or more, 0.24 or more, 0.25 or more, or 0.27 or more.
• the measurement method and conditions for the value represented by the formula P ⁇ Q / R are described in the examples.
• Alkali-soluble polymer is a polymer that can be dissolved in an alkaline substance.
• the photosensitive resin composition preferably has a carboxyl group, more preferably a copolymer containing a carboxyl group-containing monomer as a copolymerization component, from the viewpoint of alkali developability.
• the photosensitive resin composition has an aromatic group as an alkali-soluble polymer (A) from the viewpoint of high resolution and sword shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern. It is preferable to include a copolymer having an aromatic group, and it is particularly preferable to include a copolymer having an aromatic group in the side chain. Examples of such an aromatic group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group.
• the proportion of the copolymer having an aromatic group in the component (A) is preferably 50% by mass or more, preferably 60% by mass or more, preferably 70% by mass or more, preferably 80% by mass or more, preferably 90%. It may be 100% by mass or more.
• the copolymerization ratio of the comonomer having an aromatic group in the copolymer having an aromatic group is preferably Is 20% by mass or more, preferably 30% by mass or more, preferably 40% by mass or more, preferably 50% by mass or more, preferably 60% by mass or more, preferably 70% by mass or more, preferably 80% by mass or more.
• the copolymerization ratio is 95 mass% or less, More preferably, it is 90 mass% or less.
• Examples of the comonomer having an aromatic group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene). Dimer, styrene trimer, etc.).
• a monomer having an aralkyl group or styrene is preferable, and a monomer having an aralkyl group is more preferable.
• Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding benzyl group), a substituted or unsubstituted benzyl group, and the like, and a substituted or unsubstituted benzyl group is preferable.
• Examples of the comonomer having a phenylalkyl group include phenylethyl (meth) acrylate.
• Examples of the comonomer having a benzyl group include (meth) acrylates having a benzyl group, such as benzyl (meth) acrylate, chlorobenzyl (meth) acrylate, etc .; vinyl monomers having a benzyl group, such as vinylbenzyl chloride, vinylbenzyl alcohol, etc. Is mentioned. Of these, benzyl (meth) acrylate is preferred.
• the copolymer having an aromatic group (preferably a benzyl group) in the side chain includes a monomer having an aromatic group, at least one first monomer described later, and / or at least one second monomer described later. It is preferable to obtain by polymerizing.
• the alkali-soluble polymer (A) other than the copolymer having an aromatic group in the side chain is preferably obtained by polymerizing at least one of the first monomers described later, and at least one of the first monomers and More preferably, it is obtained by copolymerizing at least one second monomer described below.
• the first monomer is a monomer having a carboxyl group in the molecule.
• the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, maleic acid half ester, and the like.
• (meth) acrylic acid is preferable.
• (meth) acrylic acid means acrylic acid or methacrylic acid
• (meth) acryloyl group” means acryloyl group or methacryloyl group
• the copolymerization ratio of the first monomer is preferably 10 to 50% by mass based on the total mass of all monomer components. Setting the copolymerization ratio to 10% by mass or more is preferable from the viewpoint of developing good developability and controlling the edge fuse property. Setting the copolymerization ratio to 50% by mass or less is preferable from the viewpoint of the high resolution and sword shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern. In these viewpoints, 30% by mass is preferable. The following is more preferable, 25% by mass or less is further preferable, 22% by mass or less is particularly preferable, and 20% by mass or less is most preferable.
• the second monomer is non-acidic and has at least one polymerizable unsaturated group in the molecule.
• the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert -(Meth) acrylates such as butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; And vinyl alcohol esters; and (meth) acrylonitrile.
• the alkali-soluble polymer is prepared by polymerizing the monomer or monomers described above by a known polymerization method, preferably addition polymerization, more preferably radical polymerization. be able to.
• a monomer having an aralkyl group and / or containing styrene as a monomer is preferable from the viewpoint of chemical resistance, adhesion, high resolution, or sedge shape of a resist pattern, and includes, for example, methacrylic acid, benzyl methacrylate, and styrene.
• a copolymer, a copolymer of methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene is preferable.
• the glass transition temperature Tg of the whole mixture is preferably 110 ° C. or lower, 107 ° C. or lower, 105 ° C. or lower, 100 ° C. or lower, 95 More preferably, it is not higher than 90 ° C, not higher than 90 ° C or not higher than 80 ° C.
• the lower limit of the glass transition temperature (Tg) of the alkali-soluble polymer is not limited, but is preferably 30 ° C. or higher, more preferably 50 ° C. or higher, more preferably from the viewpoint of controlling the edge fuse property. Is 60 ° C. or higher.
• the acid equivalent of the alkali-soluble polymer (when the component (A) contains a plurality of types of copolymers, the acid equivalent of the entire mixture) is the development resistance of the photosensitive resin layer and the resist pattern solution. It is preferably 100 or more from the viewpoint of image properties and adhesion, and is preferably 600 or less from the viewpoint of developability and peelability of the photosensitive resin layer.
• the acid equivalent of the alkali-soluble polymer is more preferably from 200 to 500, and even more preferably from 250 to 450.
• the weight average molecular weight of the alkali-soluble polymer (when the component (A) includes a plurality of types of copolymers, the weight average molecular weight of the entire mixture) is preferably 5,000 to 500,000. .
• the weight average molecular weight of the alkali-soluble polymer is preferably 5,000 or more from the viewpoint of maintaining the thickness of the dry film resist uniformly and obtaining resistance to the developer. From the viewpoint of maintaining, the high resolution of the resist pattern, the viewpoint of the sword shape, and the chemical resistance of the resist pattern, it is preferably 500,000 or less.
• the weight average molecular weight of the alkali-soluble polymer is more preferably 10,000 to 200,000, further preferably 20,000 to 130,000, particularly preferably 30,000 to 100,000, most preferably 40. , 70,000.
• the degree of dispersion of the alkali-soluble polymer is preferably 1.0 to 6.0.
• the content of the (A) alkali-soluble polymer in the photosensitive resin composition is based on the total solid content of the photosensitive resin composition (hereinafter, unless otherwise specified, the same for each component). Preferably 10% to 90% by weight, more preferably 20% to 80% by weight, and still more preferably 40% to 60% by weight.
• the content of the alkali-soluble polymer is preferably 10% by mass or more from the viewpoint of maintaining the alkali developability of the photosensitive resin layer, and the resist pattern formed by exposure has performance as a resist material.
• It is preferably 90% by mass or less, more preferably 70% by mass or less from the viewpoint of sufficiently exerting, the high resolution of the resist pattern and the viewpoint of the sword shape, and further from the viewpoint of chemical resistance of the resist pattern. Preferably, it is 60 mass% or less.
• a compound having an ethylenically unsaturated bond is a compound having polymerizability by having an ethylenically unsaturated group in its structure.
• the photosensitive resin composition according to the present embodiment includes (B) an ethylenically unsaturated compound as a compound having an ethylenically unsaturated bond. It is preferable to include a (meth) acrylate compound having 3 or more bonds. In this case, the ethylenically unsaturated bond is more preferably derived from a methacryloyl group.
• Examples of the (meth) acrylate compound having three or more ethylenically unsaturated bonds include a (meth) acrylate compound having an ethylene oxide chain and a dipentaerythritol skeleton, or (b1) a compound having at least three methacryloyl groups. Is done.
• the photosensitive resin composition according to the present embodiment includes (B) an ethylenically unsaturated compound as a compound having an ethylenically unsaturated bond. It is preferable to include a (meth) acrylate compound having 5 or more bonds and having an alkylene oxide chain.
• the ethylenically unsaturated bond is more preferably derived from a methacryloyl group, and the alkylene oxide chain is more preferably an ethylene oxide chain.
• the (meth) acrylate compound having 5 or more ethylenically unsaturated bonds and having an alkylene oxide chain will be described later as, for example, a (meth) acrylate compound having an ethylene oxide chain and a dipentaerythritol skeleton.
• the concentration of the methacryloyl group in the compound (B) having an ethylenically unsaturated bond is preferably 0.20 mol / 100 g or more. Preferably it is 0.30 mol / 100g or more, More preferably, it is 0.35 mol / 100g or more, Most preferably, it is 0.40 mol / 100g or more.
• the upper limit of the concentration of the methacryloyl group is not limited as long as the polymerizability and the alkali developability are ensured, and may be, for example, 0.90 mol / 100 g or less or 0.80 mol / 100 g or less.
• the value of (B) concentration of methacryloyl group / (concentration of methacryloyl group + concentration of acryloyl group) in the compound having an ethylenically unsaturated bond is preferably 0.50 or more, more preferably 0. .60 or more, more preferably 0.80 or more, particularly preferably 0.90 or more, and most preferably 0.95 or more.
• the concentration of the ethylene oxide unit in the compound having (B) an ethylenically unsaturated bond is preferably 0.80 mol / 100 g or more, More preferably, it is 0.90 mol / 100g or more, More preferably, it is 1.00 mol / 100g or more, Especially preferably, it is 1.10 mol / 100g or more.
• the upper limit of the concentration of the ethylene oxide unit is not limited as long as the chemical resistance, adhesion, and resolution of the resist pattern are ensured. For example, 1.60 mol / 100 g or less, 1.50 mol / 100 g or less, It may be 1.45 mol / 100 g or less or 1.40 mol / 100 g or less.
• the photosensitive resin composition includes (B) an alkylene oxide chain as a compound having an ethylenically unsaturated bond. It is preferable to include a (meth) acrylate compound having a dipentaerythritol skeleton.
• the alkylene oxide chain include an ethylene oxide chain, a propylene oxide chain, a butylene oxide chain, a pentylene oxide chain, and a hexylene oxide chain.
• the photosensitive resin composition includes a plurality of alkylene oxide chains, they may be the same as or different from each other.
• the alkylene oxide chain is more preferably an ethylene oxide chain, a propylene oxide chain, or a butylene oxide chain, still more preferably an ethylene oxide chain or a propylene oxide chain, and particularly preferably an ethylene oxide chain.
• (A) an alkali-soluble polymer and a (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton are used in combination, whereby the chemical resistance, adhesion and resolution of the resist pattern are obtained. Gender balance tends to be maintained.
• the (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton refers to an ester of a dipentaerythritol compound in which at least one of a plurality of hydroxyl groups is modified with an alkyleneoxy group and (meth) acrylic acid.
• Six hydroxyl groups of the dipentaerythritol skeleton may be modified with an alkyleneoxy group.
• the number of ester bonds in one molecule of the ester may be 1 to 6, and is preferably 6.
• Examples of the (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton include, for example, hexapentane having an average of 4 to 30 mol, an average of 6 to 24 mol, or an average of 10 to 14 mol of alkylene oxide added to dipentaerythritol. (Meth) acrylate is mentioned.
• each R independently represents a hydrogen atom or a methyl group, and n is an integer of 0 to 30, and the total value of all n is 1 or more ⁇
• the compound represented by these is preferable.
• it is preferable that the average value of all n is 4 or more, or each n is 1 or more.
• R is preferably a methyl group.
• the content of the (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton in the photosensitive resin composition is preferably 1% by mass to 50% by mass, more preferably It is in the range of 5% to 40% by weight, more preferably 7% to 30% by weight.
• (B) ethylene based on the total solid content of the compound having an ethylenically unsaturated bond (B) 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 100% by mass of the compound having a polyunsaturated bond is a compound having a weight average molecular weight of 500 or more.
• the weight average molecular weight of the compound (B) having an ethylenically unsaturated bond is preferably 760 or more, more preferably 800 or more, still more preferably 830 or more, particularly Preferably it is 900 or more.
• the weight average molecular weight of the compound having an ethylenically unsaturated bond is measured by the method described in Examples.
• the photosensitive resin composition is (B) a compound having an ethylenically unsaturated bond in order to improve the flexibility of the resist pattern to improve the adhesion and to suppress the bleeding out of the constituent components of the dry film resist.
• (B1) It preferably contains a compound having at least three methacryloyl groups.
• the compound having at least three methacryloyl groups preferably has a weight average molecular weight of 500 or more, more preferably 700 or more, and still more preferably 900 or more, from the viewpoint of suppression of bleeding out.
• the number of methacryloyl groups is preferably 4 or more, 5 or more, or 6 or more.
• the compound having at least three methacryloyl groups may have an alkylene oxide chain, such as an ethylene oxide chain, a propylene oxide chain, or a combination thereof.
• trimethacrylate for example, ethoxylated glycerin trimethacrylate, ethoxylated isocyanuric acid trimethacrylate, pentaerythritol trimethacrylate, trimethylolpropane trimethacrylate (for example, trimethylolpropane average) Trimethacrylate added with 21 moles of ethylene oxide or trimethacrylate added with an average of 30 moles of ethylene oxide to trimethylolpropane is preferable from the viewpoints of flexibility, adhesion, and suppression of bleedout), etc .; , Ditrimethylolpropane tetramethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, etc.
• Penta methacrylates for example, dipentaerythritol penta methacrylate; hexamethylene dimethacrylate, for example, dipentaerythritol hexa methacrylate.
• tetra, penta or hexamethacrylate is preferable.
• pentaerythritol tetramethacrylate is preferable.
• the pentaerythritol tetramethacrylate may be tetramethacrylate in which 1 to 40 moles of alkylene oxide is added to the four terminals of pentaerythritol.
• Tetramethacrylate has the following general formula (I): ⁇ Wherein R 3 to R 6 each independently represents an alkyl group having 1 to 4 carbon atoms, X represents an alkylene group having 2 to 6 carbon atoms, m 1 , m 2 , m 3 and m 4 is each independently an integer of 0 to 40, m 1 + m 2 + m 3 + m 4 is 1 to 40, and when m 1 + m 2 + m 3 + m 4 is 2 or more, a plurality of X's may be the same or different from each other ⁇ It is more preferable that it is the tetramethacrylate compound represented by these.
• the tetramethacrylate compound represented by the general formula (I) has a group R 3 to R 6 so that the H 2 C ⁇ CH—CO—O— moiety is substituted. It is considered that the hydrolyzability in the alkaline solution is suppressed as compared with the tetraacrylate having.
• the use of the photosensitive resin composition containing the tetramethacrylate compound represented by the general formula (I) means that the resolution of the resist pattern, specifically the line shape, more specifically the line shape, and the resist It is preferable from the viewpoint of improving adhesion.
• At least one of the groups R 3 to R 6 is preferably a methyl group, and more preferably all of the groups R 3 to R 6 are methyl groups.
• X is preferably —CH 2 —CH 2 — from the viewpoint of obtaining desired resolution, sword shape and remaining film ratio for the resist pattern.
• m 1 , m 2 , m 3 and m 4 are each independently an integer of 1 to 20 Is preferable, and an integer of 2 to 10 is more preferable. Furthermore, in the general formula (I), m 1 + m 2 + m 3 + m 4 is preferably 1 to 36 or 4 to 36.
• Examples of the compound represented by the general formula (I) include pentaerythritol (poly) alkoxytetramethacrylate.
• Examples of the compound represented by the general formula (I) include compounds listed in JP2013-156369A, for example, pentaerythritol (poly) alkoxytetramethacrylate and the like.
• hexamethacrylate compound a total of 1 to 24 mol of ethylene oxide is added to the six ends of dipentaerythritol, and a total of 1 to 10 mol of ⁇ -caprolactone is added to the six ends of dipentaerythritol.
• Hexamethacrylate is preferred.
• the content of the compound (b1) having at least three methacryloyl groups exceeds 0% by mass and 16% by mass or less with respect to the total solid content of the photosensitive resin composition.
• the content is more preferably 2% by mass or more and 15% by mass or less, and further preferably 4% by mass or more and 12% by mass or less.
• the photosensitive resin composition preferably includes (B2) a compound having an ethylenically unsaturated bond and (b2) a butylene oxide chain and one or two (meth) acryloyl groups.
• B2 The compound having a butylene oxide chain and one or two (meth) acryloyl groups is preferably 500 or more, more preferably 700 or more, and still more preferably 1000 or more, from the viewpoint of suppression of bleed-out.
• Examples of the compound having a butylene oxide chain and one or two (meth) acryloyl groups include polytetramethylene glycol (meth) acrylate and polytetramethylene glycol di (meth) acrylate.
• the number of (b2) butylene oxide chains and one or two (meth) acryloyl groups is preferably 1-20, more preferably 4-15, and even more preferably 6-12. It is a (meth) acrylate or di (meth) acrylate having 1 C 4 H 8 O.
• the content of the compound having (b2) butylene oxide chain and one or two (meth) acryloyl groups exceeds 0% by mass and 20% by mass with respect to the total solid content of the photosensitive resin composition The following is preferable.
• the photosensitive resin composition may include (b3) a compound having an aromatic ring and an ethylenically unsaturated bond as a compound having (B) an ethylenically unsaturated bond.
• the compound having an aromatic ring and an ethylenically unsaturated bond may further have an alkylene oxide chain.
• the aromatic ring is preferably incorporated in the compound as a divalent skeleton derived from bisphenol A, a divalent skeleton derived from naphthalene, or a divalent aromatic group such as phenylene or methylphenylene.
• the alkylene oxide chain may be an ethylene oxide chain, a propylene oxide chain, or a combination thereof.
• the ethylenically unsaturated bond is preferably incorporated in the compound as a (meth) acryloyl group.
• the compound (b3) having an aromatic ring and an ethylenically unsaturated bond the following general formula (II): ⁇ Wherein, R 1 and R 2 each independently represent a hydrogen atom or a methyl group, A is C 2 H 4 , B is C 3 H 6 , and n 1 and n 3 are each independently N is an integer from 1 to 39, n 1 + n 3 is an integer from 2 to 40, n 2 and n 4 are each independently an integer from 0 to 29, and n 2 + n 4 is an integer from 0 to 30
• the arrangement of the repeating units of-(AO)-and-(BO)- may be random or block.
• -(AO)-and- Any of (B—O) — may be on the bisphenyl group side.
• the compound represented by these can be used.
• polyethylene glycol dimethacrylate having an average of 5 moles of ethylene oxide added to both ends of bisphenol A and polyethylene glycol having an average of 2 moles of ethylene oxide added to both ends of bisphenol A, respectively.
• diglycolate of polyethylene and polyethylene glycol dimethacrylate in which 1 mol of ethylene oxide is added to both ends of bisphenol A on average are respectively preferred.
• a compound in which the aromatic ring in the general formula (II) has a hetero atom and / or a substituent may be used.
• the hetero atom include a halogen atom
• examples of the substituent include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a phenacyl group.
• substituents may form a condensed ring, or a hydrogen atom in these substituents may be substituted with a hetero atom such as a halogen atom.
• the aromatic ring in the general formula (II) has a plurality of substituents, the plurality of substituents may be the same or different.
• the content of the compound (b3) having an aromatic ring and an ethylenically unsaturated bond exceeds 0% by mass and 50% by mass or less with respect to the total solid content of the photosensitive resin composition. If this content exceeds 0% by mass, resolution and adhesion tend to be improved, and from the viewpoint of development time and edge fusion, 50% by mass or less is preferable.
• the (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton and the (b1) to (b3) compounds described above can be used independently or in combination.
• the photosensitive resin composition includes (B) (meth) acrylate compounds having an alkylene oxide chain and a dipentaerythritol skeleton and (b1) to (b3) compounds as compounds having an ethylenically unsaturated bond, as well as other compounds. Compounds may also be included.
• Other compounds include acrylate compounds having at least one (meth) acryloyl group, (meth) acrylates having urethane bonds, compounds obtained by reacting polyhydric alcohols with ⁇ , ⁇ -unsaturated carboxylic acids, glycidyl Examples thereof include compounds obtained by reacting a group-containing compound with an ⁇ , ⁇ -unsaturated carboxylic acid, phthalic acid compounds, and the like. Among them, an acrylate compound having at least two (meth) acryloyl groups is preferable from the viewpoint of resolution, adhesion, and peeling time.
• the acrylate compound having at least two (meth) acryloyl groups may be di, tri, tetra, penta, hexa (meth) acrylate and the like.
• polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, di (meth) acrylate having both ethylene oxide and polypropylene oxide for example, “FA-023M, FA-024M, FA-027M, product name, Hitachi "Made by Kasei Kogyo” is preferred from the viewpoints of flexibility, resolution, adhesion and the like.
• ethylenically unsaturated bonds such as 4-normalnonylphenoxyoctaethylene glycol acrylate, 4-normalnonylphenoxytetraethylene glycol acrylate, and ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-methacryloyloxyethyl-schreib-phthalate
• 4-normalnonylphenoxyoctaethylene glycol acrylate 4-normalnonylphenoxytetraethylene glycol acrylate
• ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-methacryloyloxyethyl- Brighton-phthalate When one compound is contained, it is preferable from the viewpoints of peelability and cured film flexibility, and when ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ ′-methacryloyloxyethyl- GmbH-phthalate is contained, sensitivity, resolution, or adhesion is included. From the viewpoint of safety.
• the total content of all the (B) compounds having an ethylenically unsaturated bond is preferably 1% by mass to 70% by mass, more preferably 2% by mass to 60% by mass, and still more preferably 4% by mass to 50% by mass. It is in the range of mass%.
• the photopolymerization initiator is a compound that polymerizes a monomer by light.
• the photosensitive resin composition contains (C) a compound generally known in the art as a photopolymerization initiator.
• the total content of the photopolymerization initiator (C) in the photosensitive resin composition is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and still more preferably 0.1% by mass. % To 7% by mass, particularly preferably in the range of 0.1% to 6% by mass.
• the total content of the photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and sufficiently transmits light to the bottom surface of the resist to provide good high resolution. It is preferable that it is 20 mass% or less from a viewpoint of obtaining.
• Photopolymerization initiators include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoic acid esters, oxime esters
• Acridines for example, 9-phenylacridine, bisacridinylheptane, 9- (p-methylphenyl) acridine, 9- (m-methylphenyl) acridine are preferred in terms of sensitivity, resolution, and adhesion
• hexaarylbiimidazole, pyrazoline compounds, anthracene compounds for example, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, and 9,10-diphenylanthracene have sensitivity, resolution, and adhesion properties).
• Coumarin Compound for example, 7-diethylamino-4-methylcoumarin is preferable in terms of sensitivity, resolution, and adhesion
• N-aryl amino acid or an ester compound thereof for example, N-phenylglycine is sensitivity, resolution, and
• halogen compounds for example, tribromomethylphenylsulfone.
• 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyl -Diphenyl-phosphine oxide, triphenylphosphine oxide, etc. may be used.
• aromatic ketones examples include benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], 4,4′-bis (diethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzophenone. Can do. These can be used alone or in combination of two or more. Among these, 4,4'-bis (diethylamino) benzophenone is preferable from the viewpoint of adhesion. Furthermore, from the viewpoint of transmittance, the content of aromatic ketones in the photosensitive resin composition is preferably 0.01% by mass to 0.5% by mass, more preferably 0.02% by mass to 0.3%. It is in the range of mass%.
• hexaarylbiimidazole examples include 2- (o-chlorophenyl) -4,5-diphenylbiimidazole, 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ', 5'-diphenylbiimidazole, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylbiimidazole, 2,4,5-tris- (o-chlorophenyl) ) -Diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -biimidazole, 2,2′-bis- (2-fluorophenyl) -4,4 ′ , 5,5′-tetrakis- (3-methoxyphenyl) -biimid
• the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.05% by mass to 7% by mass from the viewpoint of improving the peeling characteristics and / or sensitivity of the photosensitive resin layer. %, More preferably in the range of 0.1% to 6% by weight, and still more preferably in the range of 1% to 4% by weight.
• the photosensitive resin composition preferably also contains a pyrazoline compound as a photosensitizer.
• Examples of the pyrazoline compound include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-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-isopropyl) Phenyl) -pyrazoline, 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -
• the photosensitive resin composition may contain one or more pyrazoline compounds as a photosensitizer.
• the content of the photosensitizer in the photosensitive resin composition is preferably 0.05% by mass to 5% by mass from the viewpoint of improving the peeling property and / or sensitivity of the photosensitive resin layer. More preferably, it is within the range of 0.1% by mass to 3% by mass.
• the photosensitive resin composition may contain additives such as dyes, plasticizers, antioxidants, and stabilizers as desired.
• additives listed in JP2013-156369A may be used.
• the photosensitive resin composition contains tris (4-dimethylaminophenyl) methane [leuco crystal violet] and / or diamond green (Eisen (Hodogaya Chemical Co., Ltd.) as a dye. Registered trademark) DIAMOND GREEN GH).
• the content of the dye in the photosensitive resin composition is preferably 0.001% by mass to 3% by mass, more preferably 0.01% by mass to 2% by mass, and still more preferably 0.02% by mass. % To 1% by mass.
• the content of the dye is preferably 0.001% by mass or more from the viewpoint of obtaining good colorability, and preferably 3% by mass or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.
• the photosensitive resin composition is used as a stabilizer, for example, a radical polymerization inhibitor such as a nitrosophenylhydroxyamine aluminum salt, p-methoxyphenol, 4- tert-butylcatechol, 4-ethyl-6-tert-butylphenol and the like; benzotriazoles such as 1- (2-di-n-butylaminomethyl) -5-carboxylbenzotriazole and 1- (2-di-n -Butylaminomethyl) -6-carboxylbenzotriazole 1: 1 mixture, etc .; carboxybenzotriazoles such as 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole 6-carboxy-1,2,3-benzotriazole and the like; and glycidyl Alkylene oxide compound having, for example, neopentyl glycol diglycidyl ether;
• a radical polymerization inhibitor such as a nitros
• 2-mercaptobenzimidazole 1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 2-amino-5-mercapto-1,3,4-thiadiazole, 3-amino-5-mercapto-1, Including 2,4-triazole, 3-mercapto-1,2,4-triazole, 3-mercaptotriazole, 4,5-diphenyl-1,3-diazol-2-yl, 5-amino-1H-tetrazole and the like May be.
• the total content of all stabilizers in the photosensitive resin composition is preferably 0.001% by mass to 3% by mass, more preferably 0.01% by mass to 1% by mass, and still more preferably. Is in the range of 0.05 mass% to 0.7 mass%.
• the total content of the stabilizer is preferably 0.001% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and from the viewpoint of maintaining the sensitivity of the photosensitive resin layer. It is preferable that it is 3 mass% or less.
• the photosensitive resin composition preparation liquid can be formed by adding a solvent to the photosensitive resin composition.
• Suitable solvents include ketones such as methyl ethyl ketone (MEK); and alcohols such as methanol, ethanol, isopropyl alcohol and the like. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation liquid is 500 mPa ⁇ second to 4000 mPa ⁇ second at 25 ° C.
• the photosensitive resin laminated body which has a support body and the photosensitive resin layer which consists of the said photosensitive resin composition laminated
• the photosensitive resin laminate may have a protective layer on the side opposite to the support side of the photosensitive resin layer.
• the support is not particularly limited, but is preferably a transparent one that transmits light emitted from the exposure light source.
• a support include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, Examples include polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. These films may be stretched as necessary.
• the haze is preferably 0.01% to 5.0%, more preferably 0.01% to 2.5%, and still more preferably 0.01% to 1.0%.
• an important characteristic of the protective layer used in the photosensitive resin laminate is that the protective layer is smaller than the support in terms of adhesion to the photosensitive resin layer and can be easily peeled off.
• a protective layer a polyethylene film, a polypropylene film, etc. are preferable, for example.
• a film having excellent peelability described in JP-A-59-202457 can be used.
• the thickness of the protective layer is preferably 10 ⁇ m to 100 ⁇ m, more preferably 10 ⁇ m to 50 ⁇ m.
• the thickness of the photosensitive resin layer in the photosensitive resin laminate is preferably 5 ⁇ m to 100 ⁇ m, more preferably 7 ⁇ m to 60 ⁇ m. As the thickness of the photosensitive resin layer is smaller, the resolution of the resist pattern is improved. On the other hand, the larger the thickness is, the more the strength of the cured film is improved.
• a known method may be used as a method for preparing a photosensitive resin laminate by sequentially laminating a support, a photosensitive resin layer, and if desired, a protective layer.
• the photosensitive resin composition preparation liquid is prepared, and then coated on the support using a bar coater or a roll coater and dried, and the photosensitive resin comprising the photosensitive resin composition preparation liquid on the support. Laminate the layers. Furthermore, if desired, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.
• the resist pattern is formed by laminating a photosensitive resin layer composed of the above-described photosensitive resin composition on a support, an exposure step of exposing the photosensitive resin layer, and developing the exposed photosensitive resin layer. Development steps are preferably included in this order.
• An example of a specific method for forming a resist pattern in the present embodiment is shown below.
• a photosensitive resin layer is formed on a substrate using a laminator. Specifically, when the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heat-pressed and laminated on the substrate surface with a laminator.
• the material of the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and the like.
• the photosensitive resin layer may be laminated on only one surface of the substrate surface, or may be laminated on both surfaces as necessary.
• the heating temperature during lamination is generally 40 ° C to 160 ° C.
• substrate of the resist pattern obtained can be improved by performing the thermocompression bonding at the time of lamination twice or more.
• a two-stage laminator provided with two rolls may be used, or the lamination of the substrate and the photosensitive resin layer may be repeated several times and passed through the roll.
• the photosensitive resin assembly layer is exposed to active light using an exposure machine.
• the exposure can be performed after peeling the support, if desired.
• the exposure amount is determined by the light source illuminance and the exposure time, and may be measured using a light meter.
• direct imaging exposure may be performed.
• direct imaging exposure exposure is performed directly on a substrate by a drawing apparatus without using a photomask.
• the light source a semiconductor laser having a wavelength of 350 nm to 410 nm or an ultrahigh pressure mercury lamp is used.
• the drawing pattern is controlled by a computer, the exposure amount is determined by the illuminance of the exposure light source and the moving speed of the substrate. You may perform exposure by projecting the image of a photomask through a lens.
• the unexposed or exposed portion of the exposed photosensitive resin layer is removed with a developer using a developing device. If there is a support on the photosensitive resin layer after exposure, this is excluded. Subsequently, an unexposed portion or an exposed portion is developed and removed using a developer composed of an alkaline aqueous solution to obtain a resist image.
• an aqueous solution of Na 2 CO 3 , K 2 CO 3 or the like is preferable.
• the alkaline aqueous solution is selected according to the characteristics of the photosensitive resin layer, and an aqueous Na 2 CO 3 solution having a concentration of 0.2% by mass to 2% by mass is generally used.
• a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed.
• the temperature of the developer in the development process is preferably kept constant within a range of 20 ° C. to 40 ° C.
• a heating process can be further performed at 100 ° C. to 300 ° C. if desired. By performing this heating step, the chemical resistance of the resist pattern can be improved.
• a heating furnace using hot air, infrared rays, or far infrared rays can be used for the heating step.
• the photosensitive resin composition of the present embodiment can be suitably used for forming a printed circuit board.
• a subtractive process and a semi-additive process (SAP) are used as a circuit formation method for a printed circuit board.
• the subtractive process is a method of forming a circuit by removing only a non-circuit portion from a conductor disposed on the entire surface of a substrate by etching.
• SAP is a method in which a resist is formed on a non-circuit portion on a conductor seed layer disposed on the entire surface of a substrate, and then only a circuit portion is formed by plating.
• the photosensitive resin composition is more preferably used for SAP.
• the elongation of the cured product of the photosensitive resin composition is preferably 1 mm or more, more preferably 2 mm or more, and more preferably 3 mm or more in order to improve the flexibility of the resist pattern. More preferably.
• the degree of elongation of the cured product was obtained by exposing the photosensitive resin laminate produced using the photosensitive resin composition through a rectangular mask of 5 mm ⁇ 40 mm, and developing the photosensitive resin laminate in a time twice as long as the minimum development time. It is measured by pulling the cured resist with a tensile tester (Orientec Co., Ltd., RTM-500) at a speed of 100 mm / min.
• a tensile tester Orientec Co., Ltd., RTM-500
• the Young modulus of the cured product of the photosensitive resin composition is preferably in the range of 1.5 GPa or more and less than 8 GPa from the viewpoint of resolution and flexibility of the resist pattern.
• “Young Modulus” can be measured by a nanoindentation method using a nanoindenter DCM manufactured by Toyo Technica Co., Ltd.
• “Young Modulus” is a method of laminating a resin composition to be measured on a substrate, exposing and developing the surface of the photosensitive resin composition on the substrate using Nanoindenter DCM manufactured by Toyo Technica Co., Ltd. taking measurement. Measurement methods include DCM Basic Hardness, Modulus, Tip Cal, Load Control.
• the Young's modulus was the value of “Modulas At Max Load”.
• the method for producing a conductor pattern includes a lamination step of laminating a photosensitive resin layer composed of the above-described photosensitive resin composition on a substrate such as a metal plate or a metal film insulating plate, an exposure step of exposing the photosensitive resin layer, and an exposure step.
• the conductor pattern manufacturing method is performed by using a metal plate or a metal film insulating plate as a substrate, forming a resist pattern by the above-described resist pattern forming method, and then performing a conductor pattern forming step.
• a conductor pattern is formed on a substrate surface (for example, a copper surface) exposed by development using a known etching method or plating method.
• the present invention is preferably applied in the following applications, for example.
• the resist pattern is further separated from the substrate with an aqueous solution having alkalinity stronger than that of the developer, whereby a wiring board having a desired wiring pattern (for example, Printed wiring board).
• a laminate of an insulating resin layer and a copper layer or a flexible substrate is used as a substrate.
• the copper layer is preferably an electroless copper plating layer containing palladium as a catalyst.
• the conductor pattern forming step is performed by a known plating method.
• the substrate is preferably a laminate of an insulating resin layer and a copper foil, and more preferably a copper-clad laminate.
• the alkaline aqueous solution for stripping (hereinafter, also referred to as “stripping solution”) is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of 2% by mass to 5% by mass, or an organic amine-based stripping solution is used. Generally used. A small amount of a water-soluble solvent may be added to the stripping solution. As a water-soluble solvent, alcohol etc. are mentioned, for example.
• the temperature of the stripping solution in the stripping step is preferably within the range of 40 ° C to 70 ° C. In order to perform SAP, it is preferable that the manufacturing method of a wiring board further includes the process of removing palladium from the obtained wiring board.
• a lead frame can be manufactured by forming a resist pattern by a resist pattern forming method using a metal plate such as copper, copper alloy, or iron-based alloy as a substrate, and then performing the following steps. First, a step of etching the substrate exposed by development to form a conductor pattern is performed. Thereafter, a desired lead frame can be obtained by performing a peeling process for peeling the resist pattern by a method similar to the method for manufacturing a wiring board.
• the resist pattern formed by the resist pattern forming method can be used as a protective mask member when processing the substrate by the sandblasting method.
• the substrate include glass, silicon wafer, amorphous silicon, polycrystalline silicon, ceramic, sapphire, and metal material.
• a resist pattern is formed on these substrates by the same method as the resist pattern forming method. Thereafter, a blasting material is sprayed from the formed resist pattern to cut to a desired depth, and a resist pattern remaining on the substrate is removed from the substrate with an alkali stripping solution or the like.
• substrate can be manufactured.
• a known blasting material may be used.
• fine particles having a particle diameter of 2 ⁇ m to 100 ⁇ m including SiC, SiO 2 , Al 2 O 3 , CaCO 3 , ZrO, glass, stainless steel and the like are generally used.
• a semiconductor package can be manufactured by forming a resist pattern on a wafer by a resist pattern forming method using a wafer on which a large-scale integrated circuit (LSI) has been formed as a substrate, and then performing the following steps. .
• LSI large-scale integrated circuit
• a step of forming a conductor pattern by performing columnar plating such as copper or solder on the opening exposed by development is performed.
• a peeling process for peeling the resist pattern is performed by a method similar to the method for manufacturing the wiring board, and further, a thin metal layer other than the columnar plating is removed by etching, thereby obtaining a desired semiconductor package.
• the photosensitive resin composition is used for the manufacture of printed wiring boards; the manufacture of lead frames for mounting IC chips; the precision processing of metal foils such as the manufacture of metal masks; ball grid arrays (BGA), chip sizes and packages.
• Manufacturing of packages such as (CSP); Manufacturing of tape substrates such as chip-on-film (COF) and tape automated bonding (TAB); Manufacturing of semiconductor bumps; and flat panels such as ITO electrodes, address electrodes, and electromagnetic wave shields It can be used for manufacturing a partition of a display.
• CSP chip-on-film
• TAB tape automated bonding
• semiconductor bumps and flat panels
• flat panels such as ITO electrodes, address electrodes, and electromagnetic wave shields
• the weight average molecular weight or number average molecular weight of the polymer is determined by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK). KF-807, KF-806M, KF-806M, KF-802.5) in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (use of calibration curve with Shodex STANDARD SM-105 manufactured by Showa Denko KK) It calculated
• an acid equivalent means the mass (gram) of the polymer which has a 1 equivalent carboxyl group in a molecule
• Hiranuma automatic titrator (COM-555) was used, and the acid equivalent was measured by potentiometric titration using a 0.1 mol / L aqueous sodium hydroxide solution.
• the glass transition temperature of the alkali-soluble polymer has the following formula (Fox formula): ⁇ Wherein, W i is the respective mass comonomers constituting the alkali-soluble polymer, Tg i is the glass transition temperature when the respective comonomers constituting the alkali-soluble polymer is a homopolymer, W total is the total mass of the alkali-soluble polymer, and n is the number of comonomer types constituting the alkali-soluble polymer.
• Tg i is the glass transition temperature of the homopolymer consisting of comonomers to form the corresponding alkali-soluble polymer
• Brandrup J. Immergut, E .; H.
• the value shown in the edit “Polymer handbook, Third edition, John Wiley & Sons, 1989, p. 209 Chapter VI“ Glass transition temperatures of polymers ” is used.
• Table 1 shows the glass transition temperature of the homopolymer consisting of comonomers to form the corresponding alkali-soluble polymer.
• a 19 ⁇ m-thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-818) was bonded as a protective layer on the surface of the photosensitive resin composition layer on which the polyethylene terephthalate film was not laminated. A laminate was obtained.
• Examples I-1 to I-16 and Comparative Examples I-1 to I-3 0.4 mm-thick copper laminated with 35 ⁇ m-rolled copper foil was used as an evaluation substrate for sensitivity, image quality, adhesion, and chemical resistance.
• the tension laminate was treated with a soft etching agent (CPE-900, manufactured by Hishoe Chemical Co., Ltd.), and the substrate surface was washed with 10 mass% H 2 SO 4 .
• a soft etching agent CPE-900, manufactured by Hishoe Chemical Co., Ltd.
• 35 ⁇ m-rolled copper was used by using an abrasive (Nippon Carlit Co., Ltd., Sac Random R (registered trademark # 220)).
• a 0.4 mm thick copper clad laminate on which the foil was laminated was jet scrubbed at a spray pressure of 0.2 MPa to produce a substrate for evaluation.
• ⁇ Laminate> Using a hot roll laminator (ALA-700, manufactured by Asahi Kasei Co., Ltd.), the photosensitive resin laminate was applied to a copper clad laminate that had been leveled and preheated to 60 ° C. while peeling the polyethylene film of the photosensitive resin laminate. A test piece was obtained by laminating at a roll temperature of 105 ° C. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.
• ALA-700 manufactured by Asahi Kasei Co., Ltd.
• Examples I-1 to I-16 and Comparative Examples I-1 to I-3 a direct drawing exposure machine (manufactured by Hitachi Via Mechanics, DE-1DH, light source: GaN blue-violet diode, main wavelength 405 ⁇ 5 nm) Then, using a stove 41 step tablet or a predetermined mask pattern for direct imaging (DI) exposure, exposure was performed under the condition of illuminance of 85 mW / cm 2 . The exposure was performed with an exposure amount at which the maximum number of remaining film steps when the exposure and development were performed using the stove 41 step tablet as a mask was 15. Further, in Examples II-1 to II-6 and Comparative Examples II-1 to II-5, using a chrome glass mask, a parallel light exposure machine (HMW-801, manufactured by Oak Manufacturing Co., Ltd.) was used. The exposure was performed with the exposure amount shown in FIG.
• a direct drawing exposure machine manufactured by Hitachi Via Mechanics, DE-1DH, light source: GaN blue-violet diode, main wavelength
• Examples I-1 to I-16 and Comparative Examples I-1 to I-3 after peeling the polyethylene terephthalate film of the exposed evaluation substrate, an alkali developing machine (manufactured by Fuji Kiko Co., Ltd., a dry film developing machine) was used. Then, a 1 mass% Na 2 CO 3 aqueous solution at 30 ° C. was sprayed for a predetermined time to dissolve and remove the unexposed portion of the photosensitive resin layer. At this time, development was carried out over twice the minimum development time to produce a cured resist pattern.
• the minimum development time refers to the shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve.
• Examples II-1 to II-6 and Comparative Examples II-1 to II-5 after removing the polyethylene terephthalate film from the photosensitive resin laminate, using a developing device manufactured by Fuji Kiko Co., Ltd., full cone Using a nozzle of the type, a 1 mass% Na 2 CO 3 aqueous solution at 30 ° C. was sprayed for a predetermined time at a developing spray pressure of 0.15 MPa, and developed to dissolve and remove unexposed portions of the photosensitive resin layer. At this time, the minimum time required for completely dissolving the photosensitive resin layer in the unexposed portion was measured as the minimum development time, and development was performed in twice the minimum development time to prepare a resist pattern. At that time, the washing process was performed at the same time as the developing process at a washing spray pressure of 0.15 MPa with a flat type nozzle.
• ⁇ Sensitivity evaluation> The substrate for sensitivity evaluation, which had passed 15 minutes after lamination, was exposed through a mask of a 41-step stove tablet. Development was carried out in a time twice as long as the minimum development time, and was ranked according to the following criteria according to the exposure amount at which the maximum number of remaining film steps was 15.
• ⁇ Resolution> The resolution evaluation substrate 15 minutes after the lamination was exposed using drawing data having a line pattern in which the width of the exposed area and the unexposed area was 1: 1. Development was performed with a development time twice the minimum development time to form a cured resist line. In Examples I-1 to I-16 and Comparative Examples I-1 to I-3, the minimum line width in which a cured resist line was normally formed was ranked as a resolution value according to the following criteria. ⁇ (Good): The resolution value is 12 ⁇ m or less. ⁇ (allowable): The resolution value exceeds 12 ⁇ m and is 17 ⁇ m or less. X (defect): The resolution value exceeds 17 ⁇ m.
• the minimum line width in which the cured resist lines were normally formed was ranked as a resolution value according to the following criteria.
• FT-IR manufactured by Thermo SCIENTIFIC, NICOLET 380
• the peak height P at a wave number of 810 cm ⁇ 1 was determined by measuring the absorbance with FT-IR before exposure.
• the reaction rate Q of the ethylenic double bond was determined by the following method.
• Direct exposure from a polyethylene terephthalate film (support layer) side of the photosensitive resin laminate using a drawing exposure machine manufactured by Hitachi Via Mechanics, DE-1DH, light source: GaN blue-violet diode (main wavelength 405 ⁇ 5 nm)). Went.
• the illuminance during exposure was 85 mW / cm 2 .
• the exposure amount at this time was the exposure amount at which the maximum number of remaining film steps when the exposure was carried out using the stove 41 step tablet as a mask and then developed by the above method was 15.
• the reaction rate Q of the ethylenic double bond of the cured resist obtained by the above operation is calculated by calculating the disappearance rate (%) of the ethylenic double bond group from the peak height before and after exposure at a wave number of 810 cm ⁇ 1. The rate Q (%) was determined.
• R is the film thickness ( ⁇ m) of the photosensitive resin layer, and P ⁇ Q / R was obtained by calculation.
• ⁇ (allowable): Adhesiveness value exceeds 13 ⁇ m and is 15 ⁇ m or less.
• X (defect) Adhesion value exceeds 15 ⁇ m.
• the evaluation substrate that had passed 15 minutes after the lamination had a ratio of the exposed portion to the unexposed portion of 1: 100. Exposure was through a chrome glass mask with a line pattern. Development was carried out in a time twice as long as the minimum development time, and the minimum line width in which a cured resist line was normally formed was defined as an adhesion value, and was ranked as follows.
• a chemical solution was prepared by mixing 100 ml of Cuprapro S2 manufactured by Atotech Japan Co., Ltd., 60 ml of 98% sulfuric acid and 840 ml of pure water.
• the resolution evaluation substrate 15 minutes after lamination was exposed using drawing data having a line pattern in which the width of the exposed area and the unexposed area was 1: 400.
• Development was carried out with a development time twice as long as the minimum development time, and immersed in a chemical heated to 40 ° C. in a beaker for 5 minutes. After immersion, the substrate was washed with pure water, and the minimum line width at which a cured resist line was normally formed was obtained as a chemical resistance value.
• Table 2 only the case where the chemical resistance value exceeds 17 ⁇ m is indicated as “x (defect)”.
• ⁇ Bleed-out> The photosensitive resin laminate wound up in a roll is stored at 23 ° C under light-shielding conditions, and the time until stickiness occurs on the support film surface (excluding the outermost layer of the roll) due to bleed out is ranked as follows: The bleed-out property was evaluated. ⁇ (Good): Time until stickiness occurs on the surface of the support film is 1 month or more ⁇ (Poor): Time until stickiness occurs on the surface of the support film is less than 1 month
• the evaluation results are shown in Tables 2 to 5 below.
• the photosensitive resin composition designed so that the chemical resistance evaluation is 17 ⁇ m or less is also excellent in resist pattern adhesion, resolution, and balance of sword shape. Moreover, when such a photosensitive resin composition is used, a short circuit can be suppressed when a wiring pattern is formed by plating.
• copper plating was performed after the chemical resistance evaluation, a short circuit was observed in the cured resist with a line width of 15 ⁇ m in the composition of Comparative Example I-1, but no short circuit was observed in the composition of Example I-1. It was inferred that defects could be reduced.

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