WO2021137468A1 - Couche de résine photosensible, et film photosensible sec et élément photosensible l'utilisant - Google Patents

Couche de résine photosensible, et film photosensible sec et élément photosensible l'utilisant Download PDF

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Publication number
WO2021137468A1
WO2021137468A1 PCT/KR2020/018172 KR2020018172W WO2021137468A1 WO 2021137468 A1 WO2021137468 A1 WO 2021137468A1 KR 2020018172 W KR2020018172 W KR 2020018172W WO 2021137468 A1 WO2021137468 A1 WO 2021137468A1
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Prior art keywords
photosensitive resin
formula
meth
resin layer
carbon atoms
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PCT/KR2020/018172
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English (en)
Korean (ko)
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장현석
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코오롱인더스트리 주식회사
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Priority claimed from KR1020190179945A external-priority patent/KR102177313B1/ko
Priority claimed from KR1020200095387A external-priority patent/KR102253142B1/ko
Application filed by 코오롱인더스트리 주식회사 filed Critical 코오롱인더스트리 주식회사
Priority to JP2022538988A priority Critical patent/JP7509885B2/ja
Priority to CN202080088795.XA priority patent/CN114902133A/zh
Publication of WO2021137468A1 publication Critical patent/WO2021137468A1/fr

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    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • 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
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (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
    • 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
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers

Definitions

  • the present invention relates to a photosensitive resin layer, a dry film photoresist using the same, and a photosensitive element.
  • the photosensitive resin composition is used in the form of dry film photoresist (DFR), liquid photoresist (Liquid Photoresist Ink), etc. used in printed circuit boards (PCB) or lead frames. .
  • DFR dry film photoresist
  • Liquid Photoresist Ink liquid photoresist
  • PCB printed circuit boards
  • PCBs printed circuit boards
  • PDP plasma display panels
  • ITO electrodes for other displays
  • bus address electrodes and black matrices
  • dry film photoresist is also widely used for the like.
  • Such, in general, dry film photoresist is often used for lamination on copper clad laminates.
  • a pretreatment process is first performed in order to laminate a copper clad laminate, which is an original material of the PCB.
  • the pretreatment process is in the order of drilling, deburing, and front face in the outer layer process, and undergoes face or pickling in the inner layer process.
  • face process bristle brush and jet pumice processes are mainly used, and soft etching and 5wt% sulfuric acid pickling can be used for pickling.
  • a dry film photoresist (hereinafter referred to as DFR) is generally laminated on the copper layer of the copper-clad laminate.
  • DFR dry film photoresist
  • a photoresist layer of DFR is laminated on the copper surface while peeling off the protective film of DFR using a laminator.
  • the lamination speed is 0.5 ⁇ 3.5 m/min
  • the temperature is 100 ⁇ 130°C
  • the roller pressure heating roll pressure is 10 ⁇ 90 psi.
  • the printed circuit board that has undergone the lamination process is left for at least 15 minutes to stabilize the board, and then is exposed to the photoresist of the DFR using a photomask having a desired circuit pattern formed thereon.
  • the photomask is irradiated with ultraviolet rays
  • polymerization of the photoresist irradiated with ultraviolet rays is initiated by the photoinitiator contained in the irradiated area.
  • oxygen in the photoresist is consumed, then the activated monomer is polymerized to cause a crosslinking reaction, and then a large amount of the monomer is consumed and the polymerization reaction proceeds.
  • the unexposed portion exists in a state where the crosslinking reaction has not progressed.
  • a developing process of removing the unexposed portion of the photoresist is performed.
  • alkali developable DFR 0.8 to 1.2 wt% of potassium carbonate and sodium carbonate aqueous solution are used as a developer.
  • the photoresist of the unexposed part is washed away by the saponification reaction of the carboxylic acid of the binder polymer and the developer in the developer, and the cured photoresist remains on the copper surface.
  • a circuit is formed through different processes according to the inner layer and outer layer processes.
  • a circuit is formed on the substrate through corrosion and peeling processes, and in the outer layer process, after plating and tenting processes, etching and solder stripping are performed, and a predetermined circuit is formed.
  • the photosensitive resin composition the sensitivity to ultra-high pressure mercury lamp or laser direct exposure is high, the resistance to the developer is increased in the developing process, so it is possible to form a high-density circuit, and it is used as a UV marker for setting the position of the substrate exposure.
  • a photosensitive resin composition that is excellent in color development, shortens the peeling time of the cured film, and has a small peeling specimen, so that the filter is not clogged.
  • the present invention relates to a photosensitive resin layer capable of implementing excellent adhesion to a substrate.
  • the present invention is to provide a dry film photoresist and a photosensitive element including the photosensitive resin layer.
  • a photopolymerizable compound comprising a trifunctional or more polyfunctional (meth)acrylate compound; and an alkali developable binder resin; wherein, when a tape peeling test is performed using a peel tester for a film sample in which the photosensitive resin layer is laminated on a substrate, the photosensitive resin layer has an adhesion of 90% or more as defined by Equation 1 below.
  • Adhesion (%) (Surface area of the substrate and photosensitive resin layer after the tape peeling test / Surface area of the photosensitive resin layer in contact with the substrate before the tape peeling test) * 100.
  • the trifunctional or more multifunctional (meth)acrylate compound may have a structure in which three or more alkylene oxide groups having 1 to 10 carbon atoms and (meth)acrylate functional groups are bonded to a central group having 1 to 20 carbon atoms.
  • the trifunctional or higher polyfunctional (meth)acrylate compound may include the compound of Formula 2 above.
  • the trifunctional or higher polyfunctional (meth)acrylate compound may include a compound represented by the following Chemical Formula 2-1.
  • the following Chemical Formula 2-1 is as described below.
  • the photopolymerizable compound may further include a monofunctional (meth)acrylate compound.
  • the photopolymerizable compound may include 100 parts by weight or more of the polyfunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound.
  • the monofunctional (meth)acrylate compound may include (meth)acrylate including an alkylene oxide group having 1 to 10 carbon atoms.
  • the monofunctional (meth)acrylate compound may include the compound of Formula 1 above.
  • the photopolymerizable compound may include a monofunctional (meth)acrylate compound including (meth)acrylate including an alkylene oxide group having 1 to 10 carbon atoms; and a trifunctional or more polyfunctional (meth)acrylate compound having a structure in which at least three alkylene oxide groups and (meth)acrylate functional groups having 1 to 10 carbon atoms are bonded to a central group having 1 to 20 carbon atoms; can
  • the alkali developable binder resin may have a weight average molecular weight of 20000 g/mol or more and 150000 g/mol or less.
  • polyfunctional (meth)acrylate compound 30 parts by weight or more and 90 parts by weight or less of the polyfunctional (meth)acrylate compound may be included with respect to 100 parts by weight of the monofunctional (meth)acrylate compound.
  • the alkali developable binder resin is a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), a repeating unit represented by the following formula (5), a repeating unit represented by the following formula (6), and a repeating unit represented by the following formula (7)
  • a first alkali developable binder resin including a repeating unit; and a second alkali developable binder resin including a repeating unit represented by the following Chemical Formula 4, a repeating unit represented by the following Chemical Formula 5, and a repeating unit represented by the following Chemical Formula 6; Formulas 3 to 7 are as described below.
  • 500 parts by weight or more and 1000 parts by weight or less of the second alkali developable binder resin may be included with respect to 100 parts by weight of the first alkali developable binder resin.
  • a glass transition temperature ratio of the first alkali developable binder resin and the second alkali developable binder resin may be 1:1.5 or more and 1:5 or less.
  • An acid value ratio of the first alkali developable binder resin and the second alkali developable binder resin may be 1:1.01 or more and 1:1.5 or less.
  • the thickness of the photosensitive resin layer may be 1 ⁇ m or more and 1000 ⁇ m or less.
  • the cross-sectional area of the photosensitive resin layer may be 0.10 cm 2 or more and 5.00 cm 2 or less.
  • a dry film photoresist comprising a photosensitive resin layer containing the photosensitive resin composition.
  • a polymer substrate and the photosensitive resin layer formed on the polymer substrate, a photosensitive element is provided.
  • a polymer substrate and a photosensitive resin layer formed on the polymer substrate, wherein in a tape peeling test using a peel tester on a film sample in which the photosensitive resin layer is laminated on the substrate, the adhesion degree defined by Equation 1 below is 90% or more A photosensitive element is provided.
  • Adhesion (%) (Surface area of the substrate and photosensitive resin layer after the tape peeling test / Surface area of the photosensitive resin layer in contact with the substrate before the tape peeling test) * 100.
  • first component may be referred to as a second component
  • second component may be referred to as a first component
  • substitution means that another functional group is bonded instead of a hydrogen atom in the compound, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, the position where the substituent is substituted, is not limited, and when two or more substituted , two or more substituents may be the same as or different from each other.
  • substituted or unsubstituted refers to deuterium; halogen group; cyano group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amide group; primary amino group; carboxyl group; sulfonic acid group; sulfonamide group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; alkoxysilylalkyl group; an arylphosphine group; or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consist
  • a substituent in which two or more substituents are connected may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are connected.
  • (meth) acryl is meant to include both acryl and methacryl.
  • (meth)acrylate is meant to include both acrylate and methacrylate.
  • the alkyl group is a monovalent functional group derived from an alkane, and may be straight-chain or branched, and the number of carbon atoms in the straight-chain alkyl group is not particularly limited, but is preferably 1 to 20. In addition, the number of carbon atoms of the branched chain alkyl group is 3 to 20.
  • alkyl group examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-non
  • the aryl group is a monovalent functional group derived from arene, and is not particularly limited, but preferably has 6 to 20 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group.
  • the aryl group may be a monocyclic aryl group such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto.
  • the polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.
  • the aryl group may be substituted or unsubstituted, and when substituted, examples of the substituent are as described above.
  • the alkylene group is a divalent functional group derived from an alkane, and the description of the above alkyl group may be applied, except that these are divalent functional groups.
  • a linear or branched type it may be a methylene group, an ethylene group, a propylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a pentylene group, a hexylene group, and the like.
  • the alkylene group may be substituted or unsubstituted.
  • the multivalent functional group is a residue in a form in which a plurality of hydrogen atoms bonded to any compound are removed, and examples thereof include a divalent functional group, a trivalent functional group, and a tetravalent functional group.
  • the tetravalent functional group derived from cyclobutane refers to a residue in which 4 hydrogen atoms bonded to cyclobutane are removed.
  • a direct bond or a single bond means that no atom or group of atoms is present at the corresponding position, and thus is connected by a bonding line. Specifically, it refers to a case in which a separate atom does not exist in the portion represented by R a , or L b (a and b are each an integer of 1 to 20) in the formula.
  • (photo)cured product or “(photo)cured” means not only when all of the components having an unsaturated group that can be cured or crosslinked in the chemical structure are cured, crosslinked or polymerized, but also a part of it is cured , cross-linked or polymerized.
  • a photopolymerizable compound comprising a trifunctional or more polyfunctional (meth)acrylate compound; and an alkali developable binder resin; wherein, when a tape peeling test is performed using a peel tester for a film sample in which the photosensitive resin layer is laminated on a substrate, the photosensitive resin layer having an adhesion degree of 90% or more as defined by Equation 1 above This can be provided.
  • the present inventors confirmed through experiments that the photosensitive resin layer of one embodiment can secure excellent physical properties (resolution, fine wire adhesion, etc.) as the adhesion defined by Equation 1 is 90% or more, and completed the invention. .
  • the photosensitive resin layer of the present invention may include an alkali developable binder resin.
  • the alkali developable binder resin may include at least two or more alkali developable binder resins. At least two or more kinds of alkali developable binder resin may mean a mixture of two or more kinds of alkali developable binder resin.
  • the at least two or more alkali developable binder resins include a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), a repeating unit represented by the following formula (5), a repeating unit represented by the following formula (6), and a repeating unit represented by the following formula (7)
  • R 3 is hydrogen
  • R 3 ' is an alkyl having 1 to 10 carbon atoms
  • R 4 is alkyl having 1 to 10 carbon atoms
  • R 5 is alkyl having 1 to 10 carbon atoms
  • Ar is an aryl having 6 to 20 carbon atoms
  • R 4 ′ is hydrogen
  • R 5 ′ is alkyl having 1 to 10 carbon atoms.
  • the first alkali developable binder resin may include a repeating unit represented by the following Chemical Formula 3, a repeating unit represented by the following Chemical Formula 4, a repeating unit represented by the following Chemical Formula 5, a repeating unit represented by the following Chemical Formula 6, and the following Chemical Formula It may include a random copolymer of the repeating unit represented by 7.
  • R 3 is hydrogen
  • R 3 ' is an alkyl having 1 to 10 carbon atoms
  • R 4 is alkyl having 1 to 10 carbon atoms
  • R 5 is alkyl having 1 to 10 carbon atoms
  • Ar is an aryl having 6 to 20 carbon atoms
  • R 4 ′ is hydrogen
  • R 5 ′ is alkyl having 1 to 10 carbon atoms.
  • alkyl having 1 to 10 carbon atoms may include methyl.
  • Ar is an aryl having 6 to 20 carbon atoms, and specific examples of the aryl having 6 to 20 carbon atoms include phenyl.
  • the repeating unit represented by Chemical Formula 4 may be a repeating unit derived from a monomer represented by the following Chemical Formula 4-1.
  • R 3 ' is alkyl having 1 to 10 carbon atoms.
  • the contents of R 3 ' are the same as those described above in Formula 4 above.
  • a specific example of the monomer represented by Formula 4-1 may include methacrylic acid (MAA).
  • the repeating unit represented by the formula (5) may be a repeating unit derived from a monomer represented by the following formula (5-1).
  • R 4 ′′ is an alkyl having 1 to 10 carbon atoms
  • R 5 ′′ is an alkyl having 1 to 10 carbon atoms.
  • the contents of R 4 ′′ and R 5 ′′ are the same as those described above in Formula 5 above.
  • Specific examples of the monomer represented by Formula 5-1 may include methylmethacrylate (MMA).
  • the repeating unit represented by the formula (6) may be a repeating unit derived from a monomer represented by the following formula (6-1).
  • Ar is aryl having 6 to 20 carbon atoms.
  • the content of Ar is the same as described above in Formula 6 above.
  • Specific examples of the monomer represented by Formula 6-1 include styrene (Styrene, SM).
  • the first alkali developable binder resin may have a weight average molecular weight of 30000 g/mol or more and 150000 g/mol or less, and a glass transition temperature of 20°C or more and 150°C or less. Accordingly, coatability, traceability, and mechanical strength of the resist itself after circuit formation of the dry film photoresist may be improved.
  • the first alkali developable binder resin may have an acid value of 140 mgKOH/g or more and 160 mgKOH/g or less.
  • the second alkali developable binder resin may have a weight average molecular weight of 20000 g/mol or more and 130000 g/mol or less, and a glass transition temperature of 30° C. or more and 160° C. or less. Accordingly, coatability, traceability, and mechanical strength of the resist itself after circuit formation of the dry film photoresist may be improved.
  • the weight average molecular weight means the weight average molecular weight in terms of polystyrene measured by the GPC method.
  • a commonly known analyzer and a detector such as a differential refraction detector and a column for analysis may be used, and the temperature generally applied Conditions, solvents, and flow rates can be applied.
  • the alkali developable binder resin is dissolved in tetrahydrofuran so as to have a concentration of 1.0 (w/w)% in THF (about 0.5 (w/w)% based on solid content), and a syringe of 0.45 ⁇ m pore size
  • THF tetrahydrofuran
  • 20 ⁇ l was injected into GPC, and tetrahydrofuran (THF) was used as the mobile phase of GPC, and was introduced at a flow rate of 1.0 mL/min, and the column was Agilent PLgel 5 ⁇ m Guard (7.5 x 50 mm) and Agilent PLgel 5 ⁇ m Mixed D (7.5 x 300 mm) were connected in series, and the Agilent 1260 Infinity II System, RI Detector was used as a detector for measurement at 40 °C.
  • the glass transition temperature was compared with the reference and the binder polymer in a Differential Scanning Calorimeter (DSC) (Perkin-Elmer, DSC-7).
  • DSC Differential Scanning Calorimeter
  • the temperature setting can be measured by maintaining the temperature at 20°C for 15 minutes and then increasing the temperature to 200°C at a heating rate of 1°C/min.
  • the acid value of the alkali developable binder resin sample about 1 g of the alkali developable binder resin, dissolve it in 50 ml of a mixed solvent (MeOH 20%, Acetone 80%), add two drops of 1%-phenolphthalein indicator, and then 0.1N-KOH The acid value was measured by titration.
  • a mixed solvent MeOH 20%, Acetone 80%
  • the first alkali developable binder resin may have an acid value of 140 mgKOH/g or more and 160 mgKOH/g or less.
  • the second alkali developable binder resin may have an acid value of 160 mgKOH/g or more and 200 mgKOH/g or less.
  • the glass transition temperature ratio of the first alkali-developable binder resin and the second alkali-developable binder resin is 1:1.5 or more and 1:5, 1:1.5 or more and 1:3, 1:1.5 or more, 1:2 It may be 1:1.5 or more and 1:1.8 or less, 1:1.5 or more and 1:75 or less, or 1:1.6 or more and 1:7 or less.
  • the acid value ratio of the first alkali developable binder resin and the second alkali developable binder resin is 1:1.01 or more and 1:1.5 or less, 1:1.01 or more and 1:1.25 or less, 1:1.01 or more and 1:1.2 or less, or It may be 1:1.01 or more and 1:1.1 or less.
  • the first alkali developable binder resin included in the photosensitive resin composition of the embodiment contains 1.2 moles or more and 3 moles or less, 1.2 moles of the repeating unit represented by the formula (4) with respect to 1 mole of the repeating unit represented by the formula (3). It may be included in an amount of 2 moles or more, 1.5 moles or more and 2 moles or less, or 1.5 moles or more and 1.6 moles or less.
  • the first alkali developable binder resin included in the photosensitive resin composition of the embodiment contains 2 moles or more and 10 moles or less of the repeating unit represented by Formula 5 with respect to 1 mole of the repeating unit represented by Formula 7, 3 It may contain more than 10 moles, not more than 3 moles, not more than 5 moles, or not more than 4 moles and not more than 5 moles.
  • the second alkali developable binder resin may include a random copolymer of a repeating unit represented by the following formula (4), a repeating unit represented by the following formula (5), and a repeating unit represented by the following formula (6).
  • R 3 ' is an alkyl having 1 to 10 carbon atoms
  • R 4 is alkyl having 1 to 10 carbon atoms
  • R 5 is alkyl having 1 to 10 carbon atoms
  • Ar is aryl having 6 to 20 carbon atoms.
  • the repeating unit represented by Chemical Formula 4 may be a repeating unit derived from a monomer represented by the following Chemical Formula 4-1.
  • R 3 ' is alkyl having 1 to 10 carbon atoms.
  • the contents of R 3 ' are the same as those described above in Formula 4 above.
  • a specific example of the monomer represented by Formula 4-1 may include methacrylic acid (MAA).
  • the repeating unit represented by the formula (5) may be a repeating unit derived from a monomer represented by the following formula (5-1).
  • R 4 ′′ is an alkyl having 1 to 10 carbon atoms
  • R 5 ′′ is an alkyl having 1 to 10 carbon atoms.
  • the contents of R 4 ′′ and R 5 ′′ are the same as those described above in Formula 5 above.
  • Specific examples of the monomer represented by Formula 5-1 may include methylmethacrylate (MMA).
  • the repeating unit represented by the formula (6) may be a repeating unit derived from a monomer represented by the following formula (6-1).
  • Ar is aryl having 6 to 20 carbon atoms.
  • the content of Ar is the same as described above in Formula 6 above.
  • Specific examples of the monomer represented by Formula 6-1 include styrene (Styrene, SM).
  • the first alkali developable binder resin is a repeating unit represented by the formula (4): a repeating unit represented by the formula (5): a repeating unit represented by the formula (6) 1: (2 or more and 5 or less): (0.2 or more and 0.9), 1: (2 or more and 3 or less): (0.5 or more and 0.9), 1: (2.5 or more and 3 or less): (0.6 or more and 0.9 or less) or 1: (2.75 or more and 3 or less): (0.6 or more and 0.75) hereinafter) may be included.
  • a repeating unit represented by the formula (4) a repeating unit represented by the formula (5): a repeating unit represented by the formula (6) 1: (2 or more and 5 or less): (0.2 or more and 0.9), 1: (2 or more and 3 or less): (0.5 or more and 0.9), 1: (2.5 or more and 3 or less): (0.6 or more and 0.9 or less) or 1: (2.75 or more and 3 or less): (0.6 or more and 0.75)
  • the second alkali developable binder resin is a repeating unit represented by Formula 4:
  • a repeating unit represented by Formula 6 is 1: (1.1 or more and 2 or less): (0.2 or more) 0.99 or less), 1: (1.5 or more and 2 or less): (0.5 or more and 0.99 or less), or 1: (1.5 or more and 1.75 or less): (0.75 or more and 0.99 or less).
  • the photosensitive resin layer of an embodiment of the present invention contains 500 parts by weight or more and 1000 parts by weight or less, 600 parts by weight or more and 800 parts by weight or less, of the second alkali developable binder resin with respect to 100 parts by weight of the first alkali developable binder resin, It may be included in an amount of 700 parts by weight or more and 800 parts by weight or less.
  • the second alkali developable binder resin when added in an excess of 500 parts by weight or more with respect to 100 parts by weight of the first alkali developable binder resin, a hydrophobic function is imparted to the photosensitive resin to increase resistance to the developer, thereby increasing circuit properties. A technical effect of improving can be implemented.
  • the alkali developable binder resin is included in an amount of 20 wt% or more and 80 wt% or less, based on the total weight of the photosensitive resin composition on a solid basis.
  • the solid content which is the basis of the weight, refers to the remaining components excluding the solvent in the photosensitive resin composition.
  • the content of the alkali developable binder resin of the present invention may be 40% by weight or more and 70% by weight or less based on the total weight of the photosensitive resin composition for forming the photosensitive resin layer. If the content of the alkali developable binder resin is less than 40% by weight with respect to the total photosensitive resin composition, there is a disadvantage of causing defects such as short circuit due to contamination of the developing end, and when it exceeds 70% by weight, adhesion and resolution, etc. There is a problem in that the circuit properties are poor.
  • the photopolymerization initiator included in the photosensitive resin layer according to the present invention is a material that initiates a chain reaction of photopolymerizable monomers by UV and other radiation, and plays an important role in curing the dry film photoresist.
  • Examples of the compound usable as the photopolymerization initiator include anthraquinone derivatives such as 2-methyl anthraquinone and 2-ethyl anthraquinone; and benzoin derivatives such as benzoin methyl ether, benzophenone, phenanthrene quinone, and 4,4'-bis-(dimethylamino)benzophenone.
  • anthraquinone derivatives such as 2-methyl anthraquinone and 2-ethyl anthraquinone
  • benzoin derivatives such as benzoin methyl ether, benzophenone, phenanthrene quinone, and 4,4'-bis-(dimethylamino)benzophenone.
  • the content of the photoinitiator is included in an amount of 2 wt% or more and 10 wt% or less, based on the solid content, based on the total weight of the photosensitive resin composition for forming the photosensitive resin layer.
  • the content of the photopolymerization initiator is within the above range, sufficient sensitivity may be obtained.
  • the solid content which is the basis of the weight, refers to the remaining components excluding the solvent in the photosensitive resin composition.
  • the photopolymerizable compound of the present invention has resistance to a developer after UV exposure to enable pattern formation.
  • the photopolymerizable compound of the present invention may include a trifunctional or more polyfunctional (meth)acrylate compound.
  • the trifunctional or more polyfunctional (meth)acrylate compound has a structure in which three or more alkylene oxide groups and (meth)acrylate functional groups each having 1 to 10 carbon atoms are bonded to a central group having 1 to 20 carbon atoms.
  • the trifunctional or more polyfunctional (meth) acrylate compound may include a polyfunctional (meth) acrylate compound represented by the following Chemical Formula 2.
  • R 4 is hydrogen or alkyl having 1 to 10 carbon atoms
  • R 5 is alkylene having 1 to 10 carbon atoms
  • R 6 is a functional group p including a central group having 1 to 20 carbon atoms
  • n2 is an integer of 1 to 20
  • p is the number of functional groups substituted for R 6 , and an integer of 3 to 10.
  • n2 is an integer of 1 to 20, an integer of 1 to 10, or an integer of 1 to 5
  • p is an integer of 3 to 10
  • p is an integer of 3 to 10, which is substituted for R 6 . It may be an integer of to 5, or an integer of 3 to 4.
  • the polyfunctional (meth)acrylate compound represented by Formula 2 is trifunctional or more than trifunctional (meth)acryl It may be a late compound.
  • the polyfunctional (meth)acrylate compound may be represented by the following Chemical Formula 2-1.
  • R 7 to R 9 are each independently alkylene having 1 to 10 carbon atoms
  • R 10 to R 12 are each independently hydrogen or alkyl having 1 to 10 carbon atoms
  • n3 to n5 are each independently an integer from 1 to 20.
  • n3 to n5 may be an integer of 1 to 20, an integer of 1 to 10, or an integer of 1 to 5.
  • Examples of the polyfunctional (meth)acrylate compound represented by Formula 2 are not particularly limited, but may be, for example, T063 (Trimethylolpropane [EO] 6 triacrylate) represented by Formula B below.
  • the photosensitive resin composition of the embodiment includes the polyfunctional (meth)acrylate compound represented by Chemical Formula 2, the photocuring rate and curing degree are improved, thereby securing contrast and implementing excellent fine wire adhesion.
  • the photosensitive resin layer of the embodiment may further include a monofunctional (meth)acrylate compound.
  • the monofunctional (meth)acrylate compound may include (meth)acrylate including an alkylene oxide group having 1 to 10 carbon atoms.
  • the photopolymerizable compound may include a monofunctional (meth)acrylate compound including (meth)acrylate including an alkylene oxide group having 1 to 10 carbon atoms; and a trifunctional or more polyfunctional (meth)acrylate compound having a structure in which at least three alkylene oxide groups and (meth)acrylate functional groups having 1 to 10 carbon atoms are bonded to a central group having 1 to 20 carbon atoms; can
  • the monofunctional (meth)acrylate compound may include a monofunctional (meth)acrylate compound represented by Formula 1 below.
  • R 1 is hydrogen or alkyl having 1 to 10 carbon atoms
  • R 2 is alkylene having 1 to 10 carbon atoms
  • R 3 is alkyl having 1 to 10 carbon atoms
  • n1 is an integer from 1 to 20, and ,
  • n1 may be an integer of 1 to 20, an integer of 1 to 10, or an integer of 5 to 10.
  • Examples of the monofunctional (meth)acrylate compound represented by Formula 1 are not particularly limited, but may be, for example, A040 (Methoxy propylene glycol [400] acrylate) represented by Formula A below.
  • the photosensitive resin layer of one embodiment includes the monofunctional (meth) acrylate compound represented by Formula 1, due to the low glass transition temperature of the monofunctional (meth) acrylate compound represented by Formula 1, dry Since the film photoresist has relatively high fluidity at the lamination temperature, an effect of improving physical adhesion to a substrate having high surface roughness and non-uniformity can be realized.
  • the photosensitive resin layer of the embodiment contains less than 100 parts by weight of the polyfunctional (meth)acrylate compound, 30 parts by weight or more and 90 parts by weight or less, 50 parts by weight based on 100 parts by weight of the monofunctional (meth)acrylate compound. It may contain more than 90 parts by weight, 50 parts by weight or more and 80 parts by weight or less, or 50 parts by weight or more and 75 parts by weight or less.
  • the photosensitive resin layer of one embodiment contains a small amount of the polyfunctional (meth)acrylate compound with respect to the monofunctional (meth)acrylate compound, the substrate of the monofunctional (meth)acrylate compound represented by Formula 1
  • the improvement of physical adhesion to the polyfunctional (meth)acrylate compound represented by Chemical Formula 2 and the improvement of fine wire adhesion are simultaneously realized, thereby exhibiting excellent developability and improving substrate adhesion, resulting in excellent physical properties (resolution, fine wire adhesion) etc) can be obtained.
  • the photosensitive resin layer of one embodiment contains 100 parts by weight or more of the polyfunctional (meth)acrylate compound with respect to 100 parts by weight of the monofunctional (meth)acrylate compound, a technical problem that substrate adhesion is lowered may occur.
  • the photopolymerizable compound may further include a bifunctional (meth)acrylate compound including alkylene glycol-based di(meth)acrylate and urethane-based di(meth)acrylate.
  • the photosensitive resin layer of the embodiment includes a photopolymerizable compound, and the photopolymerizable compound is a monofunctional (meth) acrylate compound, a polyfunctional (meth) acrylate compound, and an alkylene glycol-based di (meth) acrylate. and a bifunctional (meth)acrylate compound including urethane-based di(meth)acrylate.
  • the alkylene glycol-based di (meth) acrylate is ethylene glycol di (meth) acrylate (ethylene glycol di (meth) acrylate), diethylene glycol di (meth) acrylate (diethylene glycol di (meth) acrylate), tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate meth)acrylate), polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, ethylene glycol diglycidyl ether Di(meth)acrylate (ethylene glycol diglycidyl ether di(meth)acrylate), diethylene glycol diglycidyl ether di(meth)acrylate, Miwon Specialty Chemical Co., Ltd.
  • Miramer M244 (BPA(EO)3DA, Bisphenol A (EO)3 Diacrylate), Miramer M240 (BPA(EO)4DA, Bisphenol A (EO)4 Diacrylate), Miramer M241 (Bisphenol A (EO)4 Dimethacrylate) ), Miramer M2100 (BPA(EO)10DA, Bisphenol A (EO)10 Diacrylate), Miramer M2200 (BPA(EO)20DA, Bisphenol A (EO)20 Diacrylate), Miramer M2101 from Miwon Specialty Chemical Co., Ltd. (Bisphenol A (EO)10 Dimethacrylate), etc. can
  • KUA-1330h or the like may be used as the urethane-based di(meth)acrylate.
  • the urethane-based di(meth)acrylate may provide flexibility by having a larger molecular weight and a linear structure than the conventional simple alkylene oxide. This is a cause of improving the tenting properties required for the dry film photoresist (DFR) for the outer layer, and the hydrophobicity of polyol, one of the components of urethane acrylate, improves resistance to the plating solution, which is a strong acid, and does not contaminate the plating solution.
  • DFR dry film photoresist
  • the urethane-based di (meth) acrylate is obtained by reacting a polyether compound having a hydroxyl group or a polyester compound having a hydroxyl group and a diisocyanate compound to obtain a urethane compound, and a compound having both a hydroxyl group and an ethylenically unsaturated group with the obtained urethane compound can be obtained by reacting.
  • polyether compound having a hydroxyl group glycols such as polytetramethylene glycol, polyoxyethylene, polyoxypropylene, and polyoxytetrahydrofuran are used as polyether glycol, and as the polyester compound having a hydroxyl group, adipic acid and A compound obtained by condensing 1,4-butadiol or the like is used.
  • diisocyanate compound (a-2) examples include an aliphatic diisocyanate compound having a divalent aliphatic group such as an alkylene group, an alicyclic diisocyanate compound having a divalent alicyclic group such as cycloalkylene, an aromatic diisocyanate compound, and iso A cyanurated modified product, a carbodiimidized modified product, a biuret-ized modified product, etc. are mentioned.
  • examples of the aliphatic diisocyanate compound include hexamethylene isocyanate, trimethylhexamethylene diisocyanate, and the like.
  • alicyclic diisocyanate compound examples include isophorone diisocyanate, methylenebis(cyclohexyl)diisocyanate, 1,3- or 1,4-bis(isocyanatemethyl)cyclohexane.
  • aromatic diisocyanate compound a dimerized polymer of 2,4-toloene diisocyanate, 2,6-toloene diisocyanate, 2,4-toloene diisocyanate or 2,6-toloene diisocyanate, (o, p or m) -xylene diisocyanate, diphenylmethane diisocyanate, 1, 5- naphthalene diisocyanate, etc. are mentioned.
  • the isocyanate compound which has 2 or more isocyanate groups such as triphenylmethane triisocyanate and tris (isocyanate phenyl) thiophosphate, may be contained.
  • an alicyclic diisocyanate compound is preferable from a viewpoint of improving the flexibility and toughness of a photocured material and improving board
  • a urethane compound is prepared by reacting the polyether compound or polyester compound having the hydroxyl group with a diisocyanate compound. It is preferable to set it as 1.01-2.0 molar ratio of a diisocyanate compound with respect to 1 mol of the polyether compound or polyester compound which has a hydroxyl group in the said reaction, and it is more preferable to set it as 1.1-2.0 molar ratio. If the content of the diisocyanate compound is less than 1.01 mol or more than 2.0 mol, a urethane compound having isocyanate groups at both ends cannot be stably obtained.
  • the reaction temperature is preferably 60 to 120°C. If it is less than 60°C, the reaction tends not to proceed sufficiently, and if it exceeds 120°C, the reaction operation may be dangerous due to rapid exotherm.
  • a compound having a hydroxyl group and a (meth)acryloyl group in the molecule may be mentioned.
  • examples of such compounds include hydroxy (meth) acrylate, an ester compound prepared by reacting a caprolactone adduct or an alkylene oxide adduct of hydroxy (meth) acrylate, and (meth) acrylic acid with a polyhydric alcohol such as glycerin, and glycidyl (meth) arylate acrylic acid adducts.
  • hydroxy (meth) acrylate examples include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.
  • hydroxy (meth)acrylate As a caprolactone adduct of the said hydroxy (meth)acrylate, hydroxyethyl (meth)acrylate caprolactone adduct, hydroxypropyl (meth)acrylate caprolactone adduct, hydroxybutyl (meth)acrylate - Caprolactone adduct is mentioned, As an alkylene oxide adduct, hydroxyethyl (meth)acrylate/alkylene oxide adduct, hydroxypropyl (meth)acrylate/propylene oxide adduct, hydroxybutyl ( and meth)acrylate and butylene oxide adducts.
  • ester compound For example, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, phenerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, trimethylol propane mono( meth)acrylate, ditrimethylolpropane tri(meth)acrylate, di(meth)acrylate of an ethylene oxide adduct of trimethylolpropane, and di(meth)acrylate of a propylene oxide adduct of trimethylolpropane can These are used individually by 1 type or in combination of 2 or more types.
  • the urethane-based di(meth)acrylate is a compound derived from the addition reaction of the urethane compound with a compound having both a hydroxyl group and an ethylenically unsaturated group, and 2.0 to 2.4 a compound having both a hydroxyl group and an ethylenically unsaturated group with respect to 1 mole of the urethane compound It can be obtained by adding it in a molar ratio and carrying out addition reaction at 60-90 degreeC.
  • the urethane-based di(meth)acrylate preferably has a weight average molecular weight in the range of 1,000 to 60,000 g/mol.
  • the weight average molecular weight is less than 1,000 g/mol, it is difficult to sufficiently increase flexibility and toughness, so that substrate adhesion cannot be improved, and when it exceeds 60,000 g/mol, developability deteriorates and development time becomes slow. Therefore, the urethane-based di (meth) acrylate according to the present invention preferably has a weight average molecular weight of 1,000 to 60,000 g/mol.
  • the urethane-based di(meth)acrylate having a weight average molecular weight of 1,000 to 60,000 g/mol is included in the photosensitive resin composition in an amount of 1 to 20% by weight, preferably 1.5 to 15% by weight.
  • the content of the urethane-based di(meth)acrylate having a weight average molecular weight of 1,000 to 60,000 g/mol is less than 1% by weight, the effect is insignificant, and when it exceeds 20% by weight, the development time in the post-exposure development process There is a disadvantage in that scum and sludge are generated in large amounts as well as a sharp increase.
  • the photosensitive resin layer of one embodiment contains 1 part by weight or more and 50 parts by weight or more, 1 part by weight or more and 30 parts by weight or less of the urethane-based di(meth)acrylate with respect to 100 parts by weight of the alkylene glycol-based di(meth)acrylate, 1 part by weight or more and 10 parts by weight or less, or 1 part by weight or more and 5 parts by weight or less.
  • the photosensitive resin composition of the embodiment may reduce circuit properties or A technical effect of changing peeling and developing time can be realized.
  • the photosensitive resin layer of one embodiment contains 500 parts by weight or more and 1500 parts by weight or less, 500 parts by weight or more and 1000 parts by weight of the bifunctional (meth)acrylate compound with respect to 100 parts by weight of the polyfunctional (meth)acrylate compound. Parts by weight or less, 750 parts by weight or more and 1000 parts by weight or less, 800 parts by weight or more and 900 parts by weight or less.
  • the photosensitive resin layer of the embodiment contains 500 parts by weight or more and 1000 parts by weight or less, 500 parts by weight or more and 800 parts by weight of the bifunctional (meth)acrylate compound with respect to 100 parts by weight of the monofunctional (meth)acrylate compound.
  • 500 parts by weight or more and 750 parts by weight or less 500 parts by weight or more and 700 parts by weight or less, 500 parts by weight or more and 600 parts by weight or less.
  • the photosensitive resin layer of one embodiment contains less than 100 parts by weight of the polyfunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound, and the bifunctional (meth)acrylate
  • the compound may be included in an amount of 500 parts by weight or more and 1500 parts by weight or less.
  • the monofunctional (meth) acrylate compound, the polyfunctional (meth) acrylate compound, and the difunctional (meth) acrylate compound are included, and at the same time, as the composition satisfies the weight range, the photosensitivity of the embodiment
  • the resin composition not only realizes excellent adhesion to the substrate, but also secures contrast and can implement excellent adhesion to fine wires.
  • the monofunctional photopolymerizable compound may be included in an amount of 0.1 wt% or more and 2.5 wt% or less.
  • the polyfunctional photopolymerizable compound may be included in an amount of 2.6 wt% or more and 5.0 wt% or less.
  • the photosensitive resin composition for forming the photosensitive resin layer contains 0.1 wt% or more and 2.5 wt% or less of the monofunctional photopolymerizable compound with respect to the total weight of the photosensitive resin composition, and 2.6 wt% of the polyfunctional photopolymerizable compound It may be included in 5.0 wt% or more.
  • the compound represented by Formulas 1 and 2 when the effect according to the addition is insufficient, and the monofunctional photopolymerizable compound exceeds 2.5 wt% or the polyfunctional photopolymerizable compound exceeds 5.0 wt%, hydrophobicity increases and the development time in the developing process after exposure is rapidly increased Problems may arise.
  • the content of the photopolymerizable compound may be included in an amount of 10% by weight or more and 70% by weight or less, based on the total weight of the photosensitive resin composition based on the solid content.
  • an effect of enhancing photosensitivity, resolution, and adhesion may be obtained.
  • the photosensitive resin composition for forming the photosensitive resin layer contains 20 wt% or more and 80 wt% or less of an alkaline developable binder resin, 0.1 wt% or more and 10 wt% or less of a photopolymerization initiator, and 10 wt% or more and 70 wt% of a photopolymerizable compound based on solid content It may include the following.
  • the solid content which is the basis of the weight, refers to the remaining components excluding the solvent in the photosensitive resin composition.
  • the photosensitive resin composition may further include a solvent.
  • the solvent is generally selected from methyl ethyl ketone (MEK), methanol, THF, toluene, and acetone, and the solvent is not particularly limited, and the content is also of the photopolymerization initiator, alkali developable binder resin and photopolymerizable compound. It may be contained by adjusting according to the content.
  • the photosensitive resin composition may further include other additives as necessary.
  • the other additives include dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, and diallyl phthalate in the form of phthalic acid esters as plasticizers; triethylene glycol diacetate, tetraethylene glycol diacetate in the form of glycol esters; p-toluene sulfonamide, benzenesulfonamide, n-butylbenzenesulfonamide in acid amide form; triphenyl phosphate and the like can be used.
  • the leuco dye in order to improve the handleability of the photosensitive resin composition, you may put a leuco dye and a coloring substance.
  • the leuco dye include tris(4-dimethylamino-2-methylphenyl)methane, tris(4-dimethylamino-2methylphenyl)methane, and fluoran dye.
  • the contrast is favorable and it is preferable.
  • the content may be 0.1 wt% or more and 10 wt% or less in the photosensitive resin composition. From a viewpoint of expression of contrast, 0.1 weight% or more is preferable, and 10 weight% or less is preferable from a viewpoint of maintaining storage stability.
  • the coloring material for example, toluenesulfonic acid monohydrate, fucine, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, Malachite Green, Diamond Green, Basic Blue 20, etc.
  • the added amount may be 0.001% by weight or more and 1% by weight or less in the photosensitive resin composition. At a content of 0.001% by weight or more, there is an effect of improving handling, and at a content of 1% by weight or less, there is an effect of maintaining storage stability.
  • additives may further include a thermal polymerization inhibitor, a dye, a discoloring agent, an adhesion promoter, and the like.
  • the degree of adhesion defined by Equation 1 below is 90% or more, 90% or more, 100% or less, or 95% or more. It may be 100% or less.
  • the photosensitive resin layer of the embodiment includes the above-described photopolymerizable compound.
  • Adhesion (%) (Surface area of the substrate and photosensitive resin layer after the tape peeling test / Surface area of the photosensitive resin layer in contact with the substrate before the tape peeling test) * 100.
  • the photosensitive resin layer of the embodiment includes a monofunctional (meth)acrylate compound represented by Formula 1, and a polyfunctional (meth)acrylate compound represented by Formula 2, Equation 1
  • the degree of adhesion defined as may be 90% or more.
  • Equation 1 As the adhesion defined by Equation 1 is 90% or more, the effect of improving the adhesion to the substrate of the dry film photoresist including the photosensitive resin layer of the embodiment can be realized.
  • the substrate may be a reverse treated foil.
  • the surface roughness of the substrate may be 1 ⁇ m or more and 10 ⁇ m or less, 3 ⁇ m or more and 7 ⁇ m or less, or 4 ⁇ m or more and 6 ⁇ m or less.
  • the tape peeling test of Equation 1 may be performed using a peel test after attaching a standard tape to a film sample in which the photosensitive resin layer is laminated on the substrate.
  • the adhesion degree defined by Equation 1 is 90% or more, as the photosensitive resin layer of one embodiment contains an excess of the monofunctional (meth) acrylate compound with respect to the polyfunctional (meth) acrylate compound, the formula Due to the low glass transition temperature of the monofunctional (meth)acrylate compound represented by 1, it has a relatively large fluidity at the lamination temperature of the dry film photoresist, and the surface roughness is high and the physical adhesion to the non-uniform substrate is improved. can be implemented.
  • a dry film photoresist including the photosensitive resin layer of the embodiment may be provided.
  • the content of the photosensitive resin layer includes all of the content described above in the embodiment.
  • the photosensitive resin layer may include a dried product or a cured product of the photosensitive resin composition.
  • the said dried material means the substance obtained through the drying process of the photosensitive resin composition.
  • the cured product means a substance obtained through a curing step of the photosensitive resin composition.
  • the thickness of the dry film photoresist is not particularly limited, but can be freely adjusted within, for example, 0.01 ⁇ m to 1 mm. When the thickness of the dry film photoresist increases or decreases by a specific value, physical properties measured in the dry film photoresist may also change by a specific value.
  • the dry film photoresist may further include a base film and a protective film.
  • the base film serves as a support for the photosensitive resin layer during manufacturing of the dry film photoresist, and facilitates handling during exposure of the photosensitive resin layer having adhesive force.
  • various plastic films can be used, for example, an acrylic film, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, a polynorbornene (PNB) film, a cycloolefin polymer (COP) film , and may include at least one plastic film selected from the group consisting of a polycarbonate (PC) film.
  • the thickness of the base film is not particularly limited, but can be freely adjusted within, for example, 0.01 ⁇ m to 1 mm.
  • the protective film prevents damage to the resist during handling and serves as a protective cover for protecting the photosensitive resin layer from foreign substances such as dust, and is laminated on the back surface of the photosensitive resin layer on which the base film is not formed.
  • the protective film serves to protect the photosensitive resin layer from the outside, and it is easily detached when the dry film photoresist is applied in a post-process, and requires proper releasability and adhesiveness so that it does not release when stored and distributed.
  • plastic films can be used as the protective film, for example, an acrylic film, a polyethylene (PE) film, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, a polynorbornene (PNB) film, a cyclo It may include at least one plastic film selected from the group consisting of an olefin polymer (COP) film, and a polycarbonate (PC) film.
  • the thickness of the protective film is not particularly limited, but can be freely adjusted within, for example, 0.01 ⁇ m to 1 mm.
  • the method for producing the dry film photoresist is not particularly limited, for example, the photosensitive resin composition of one embodiment is coated using a conventional coating method on a conventional base film such as polyethylene terephthalate, and then dried A dry film may be prepared by laminating the dried photosensitive resin layer using a conventional protective film such as polyethylene on the upper surface.
  • a method of coating the photosensitive resin composition is not particularly limited, and for example, a method such as a coating bar may be used.
  • the drying of the coated photosensitive resin composition may be carried out by a heating means such as a hot air oven, a hot plate, a hot air circulation furnace, an infrared furnace, and may be performed at a temperature of 50° C. or more and 100° C. or less.
  • a heating means such as a hot air oven, a hot plate, a hot air circulation furnace, an infrared furnace, and may be performed at a temperature of 50° C. or more and 100° C. or less.
  • the adhesion degree defined by the following Equation 2 is 90% or more, 90% It may be 100% or more, or 95% or more and 100% or less. This may be realized as the photosensitive resin layer of the embodiment includes the above-described photopolymerizable compound.
  • Adhesion (%) (Surface area of the photosensitive resin layer of the dry film photoresist in contact with the substrate after the tape peeling test / Surface area of the photosensitive resin layer of the dry film photoresist in contact with the substrate before the tape peeling test) * 100.
  • the content of the adhesion degree includes all of the content described above.
  • Equation 2 As the adhesion defined by Equation 2 is 90% or more, the effect of improving the adhesion of the dry film photoresist to the substrate of the embodiment can be realized.
  • a photosensitive element may be provided.
  • Adhesion (%) (Surface area of the substrate and photosensitive resin layer after the tape peeling test / Surface area of the photosensitive resin layer in contact with the substrate before the tape peeling test) * 100.
  • the content of the adhesion degree includes all of the content described above.
  • the photosensitive element having excellent adhesion to the substrate may be provided.
  • the photosensitive resin layer includes an alkali developable binder resin and a photopolymerizable compound
  • the photopolymerizable compound is a monofunctional (meth) acrylate compound represented by the following formula (1), and a polyfunctional ( It may include a meth)acrylate compound.
  • R 1 is hydrogen or alkyl having 1 to 10 carbon atoms
  • R 2 is alkylene having 1 to 10 carbon atoms
  • R 3 is alkyl having 1 to 10 carbon atoms
  • n1 is an integer from 1 to 20, and ,
  • R 4 is hydrogen or alkyl having 1 to 10 carbon atoms
  • R 5 is alkylene having 1 to 10 carbon atoms
  • R 6 is a functional group p including a central group having 1 to 20 carbon atoms
  • n2 is an integer of 1 to 20
  • p is the number of functional groups substituted for R 6 , and an integer of 3 to 10.
  • the content of the photosensitive resin composition includes all of the content described above in the one embodiment and the other embodiment.
  • the photosensitive resin layer includes an alkali developable binder resin and a photopolymerizable compound
  • the photopolymerizable compound is a monofunctional (meth) acrylate compound represented by the following Chemical Formula 1, and a polyfunctional ( It may include a meth)acrylate compound.
  • R 1 is hydrogen or alkyl having 1 to 10 carbon atoms
  • R 2 is alkylene having 1 to 10 carbon atoms
  • R 3 is alkyl having 1 to 10 carbon atoms
  • n1 is an integer from 1 to 20, and ,
  • R 4 is hydrogen or alkyl having 1 to 10 carbon atoms
  • R 5 is alkylene having 1 to 10 carbon atoms
  • R 6 is a functional group p including a central group having 1 to 20 carbon atoms
  • n2 is an integer of 1 to 20
  • p is the number of functional groups substituted for R 6 , and an integer of 3 to 10.
  • various plastic films can be used, for example, an acrylic film, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, a polynorbornene (PNB) film, a cycloolefin polymer (COP) film , and may include at least one plastic film selected from the group consisting of a polycarbonate (PC) film.
  • the thickness of the polymer substrate is not particularly limited, but can be freely adjusted within, for example, 0.01 ⁇ m to 1 mm.
  • an anti-blocking layer is formed by an in-line coating method in which an unstretched polyester film is uniaxially stretched, a crude liquid containing a binder resin and organic particles is applied on one surface of the polymer substrate, and the rest is uniaxially stretched. film can be mentioned.
  • an in-line coating method was selected instead of adding an anti-blocking agent, which has been usually added in consideration of running properties and winding characteristics during manufacturing, and an organic particle layer using substitute particles that do not impair transparency. did it
  • examples of organic particles used as particles that do not impair transparency while considering running properties and winding characteristics include methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, normal butyl methacrylate, and normal butyl methyl methacrylate.
  • Acrylic particles such as a copolymer or terpolymer of acrylic acid and methacrylic acid; olefinic particles such as polyethylene, polystyrene, and polypropylene; acrylic and olefinic copolymers;
  • organic particles such as multi-layer multi-component particles in which homopolymer particles are formed and then other types of monomers are coated on the layer may be used.
  • These organic particles should be specifically spherical and have a difference in refractive index with the binder resin.
  • 'spherical' is defined as a ratio of a minor axis (a) to a major axis (b) of 0.5 ⁇ a/b ⁇ 2 in an ellipse, and a relationship with the diagonal line d in a rectangle is d2 ⁇ a2+b2.
  • the relation between the axis f with the longest distance between vertices and the c axis other than the a and b axes is defined as f2 ⁇ c2+a2+b2.
  • the shape of the particles should be spherical, which is preferable in terms of running performance.
  • the difference in refractive index between the organic particles and the binder resin is 0.05 or less. If the difference in refractive index is greater than 0.05, Haze is increased. This means that there is a lot of scattered light, and when there is a lot of such scattered light, the smoothing effect of the sidewall is reduced. It also depends on the size and quantity of organic particles. It is preferable that the organic particles have an average particle diameter of about 0.5 ⁇ m to 5 ⁇ m, and when it is smaller than this, running characteristics and winding characteristics are deteriorated, and when it is larger than 5 ⁇ m, haze is increased, and it is undesirable in consideration of the occurrence of a drop-off problem.
  • the content of the organic particles is preferably 1 to 10% by weight based on the total amount with the binder resin.
  • the content of organic particles is less than 1% by weight based on the total amount of the binder resin, the anti-blocking effect is insufficient and is weak to scratches, winding characteristics and running characteristics are deteriorated, and if it exceeds 10% by weight, haze increases and transparent characteristics There could be a problem with this getting worse.
  • inorganic particles may be added in addition to the organic particles as described above.
  • an inorganic anti-blocking agent that has been commonly used, and colloidal silica having a particle size of 100 nm or less is preferably added.
  • the content is preferably included in an amount of 10 parts by weight or less based on 100 parts by weight of the binder resin.
  • binder resin that acts as an adhesive for applying such organic particles to an unstretched polyester film
  • resins include unsaturated polyester, methyl methacrylate, acrylic resins such as ethyl methacrylate, isobutyl methacrylate, normal butyl methacrylate, normal butyl methyl methacrylate, acrylic acid, a copolymer or terpolymer of methacrylic acid; urethane-based resin; epoxy resin; Or a melamine-type resin etc. are mentioned,
  • it is an acrylic resin.
  • the solvent that can be used in the preparation of the binder resin and the organic particles is preferably water.
  • a crude liquid containing organic particles in a binder resin is uniaxially stretched on an unstretched polyester film obtained by melt-extrusion of PET pellets, and then is applied on the uniaxially stretched film.
  • the application may be performed on at least one surface of the uniaxially oriented film, and the thickness is preferably about 30 nm to 200 nm based on the thickness after final drying. If the crude liquid containing organic particles is applied thinner than 30 nm on the uniaxially stretched film, the organic particles are easily removed and are vulnerable to scratches, and there is a problem that white powder is generated. If applied thicker than 200 nm, the viscosity of the crude liquid is increased. Due to this, in-line coating with high coating speed, coating streaks occur in the coating direction.
  • the polymer substrate obtained by applying organic particles instead of a general anti-blocking agent has excellent transparency due to organic particles having excellent light transmittance while maintaining winding characteristics and running characteristics due to the particle layer. It is a base film.
  • Lamination of the photosensitive resin layer is performed on the opposite side of the layer containing organic particles in the polymer substrate.
  • an anti-blocking agent is included as before.
  • There is no crater-shaped flaw that appears as the base film is laminated. Since the particles such as silica are larger in size than organic particles and their distribution is throughout the base film, the effect of silica appears in a portion adjacent to the photosensitive resin layer, even though it is insignificant.
  • the size of the organic particles is 0.5 ⁇ m to 5 ⁇ m, and the organic particle layer is not adjacent to the photosensitive resin layer, so that the organic particles do not have a physical effect.
  • organic particles having excellent light transmittance sidewall defects can be reduced and other circuit properties are not impaired.
  • the photosensitive element may further include a protective film formed on the photosensitive resin layer.
  • the protective film prevents damage to the photosensitive resin layer during handling and serves as a protective cover for protecting the photosensitive resin layer from foreign substances such as dust, and is laminated on the back surface of the photosensitive resin layer on which the polymer substrate is not formed.
  • the protective film serves to protect the photosensitive resin layer from the outside, and when the photosensitive element is applied to a post-process, it is easily detached, and it requires proper release property and adhesiveness so as not to be released when stored and distributed.
  • plastic films can be used as the protective film, for example, an acrylic film, a polyethylene (PE) film, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, a polynorbornene (PNB) film, a cyclo It may include at least one plastic film selected from the group consisting of an olefin polymer (COP) film, and a polycarbonate (PC) film.
  • the thickness of the protective film is not particularly limited, but can be freely adjusted within, for example, 0.01 ⁇ m to 1 mm.
  • a circuit board or display device including the photosensitive resin layer containing the photosensitive resin composition of the embodiment may be provided.
  • the content of the photosensitive resin composition includes all of the content described above in the embodiment.
  • circuit board or the display device are not particularly limited, and various conventionally known technical configurations are applicable without limitation.
  • the photosensitive resin layer included in the circuit board or the display device may be in the form of a film without openings or in the form of a pattern having openings.
  • the photosensitive resin layer of the dry film photoresist of the other embodiment is laminated on a circuit board or a substrate for manufacturing a display device, followed by exposure and development.
  • the photosensitive resin layer of the dry film photoresist of the other embodiment is laminated on a circuit board or a substrate for manufacturing a display device, followed by exposure and development.
  • the dry film photoresist or photosensitive element of the other embodiment has a protective film on the photosensitive resin layer
  • a process of removing the protective film before laminating the photosensitive resin layer on a circuit board or a substrate for manufacturing a display device may be further performed.
  • the dry film photoresist or photosensitive element of the other embodiment has a polymer substrate or a base film laminated on one surface of the photosensitive resin layer, a process of removing the polymer substrate or base film immediately after the exposure process may be further performed.
  • the dry film photoresist or the photosensitive resin layer contained in the photosensitive element of the other embodiment may be included in the circuit board or the display device.
  • a photosensitive resin composition capable of implementing excellent adhesion to a substrate and a dry film photoresist using the same, a circuit board, and a display device can be provided.
  • FIG. 1 shows an optical microscope image of adhesion between a substrate and a photosensitive resin layer during a tape peeling test measured in Examples.
  • FIG. 2 shows an optical microscope image of the adhesion between the substrate and the photosensitive resin layer during the tape peeling test measured in Comparative Example 1.
  • FIG. 3 shows an optical microscope image of the adhesion between the substrate and the photosensitive resin layer during the tape peeling test measured in Comparative Example 2.
  • a mechanical stirrer and a reflux device were installed in a four-necked round-bottom flask, and then the inside of the flask was purged with nitrogen.
  • the inside of the flask was purged with nitrogen.
  • 80 g of methyl ethyl ketone (Methyl Ethyl Ketone, MEK) and 7.5 g of methanol (Methanol, MeOH) were added, and then 0.45 g of azobisisobutyronitrile (AIBN) was added and completely dissolved.
  • acrylic acid (AA) 8g, methacrylic acid (MAA) 15g, butyl acrylate (BA) 15g, methyl methacrylate (MMA) 52g, and styrene ( Styrene, SM) 10 g of a monomer mixture was added, and the temperature was raised to 80° C. and then polymerized for 6 hours to prepare alkali developable binder resin 1.
  • the alkali developable binder resin 1 was measured to have a weight average molecular weight of 71538 g/mol, a glass transition temperature of 79° C., a solid content of 51.4% by weight, and an acid value of 156.3 mgKOH/g.
  • the alkali developable binder resin is dissolved in tetrahydrofuran so as to have a concentration of 1.0 (w/w)% in THF (about 0.5 (w/w)% based on the solid content) to 0.45 ⁇ m Pore
  • tetrahydrofuran THF
  • the acid value about 1 g of the alkali developable binder resin was sampled, dissolved in 50 ml of a mixed solvent (MeOH 20%, Acetone 80%), two drops of 1%-phenolphthalein indicator were added, and then the acid value was measured by titration with 0.1N-KOH.
  • a mixed solvent MeOH 20%, Acetone 80%
  • the solid content was determined by measuring the weight percent ratio of the solid content remaining after heating at 150° C. for 120 minutes in an oven based on the weight of the alkali developable binder resin prepared in Preparation Example described above.
  • a mechanical stirrer and a reflux device were installed in a four-necked round-bottom flask, and then the inside of the flask was purged with nitrogen.
  • the inside of the flask was purged with nitrogen.
  • 80 g of methyl ethyl ketone (Methyl Ethyl Ketone, MEK) and 7.5 g of methanol (Methanol, MeOH) were added, and then 0.9 g of azobisisobutyronitrile (AIBN) was added and completely dissolved.
  • alkali developable binder resin 2 (weight average molecular weight 39000 g/mol, glass transition temperature 128 °C, solid content 45.6 wt%, acid value 163.1 mgKOH/g) was prepared.
  • the photopolymerization initiators are dissolved in methyl ethyl ketone (MEK) as a solvent, the photopolymerizable compound and the alkali developable binder resin are added, and the photosensitive resin is mixed for about 1 hour using a mechanical stirrer.
  • MEK methyl ethyl ketone
  • the obtained photosensitive resin composition was coated on a 29 ⁇ m PET film using a coating bar.
  • the coated photosensitive resin composition layer was dried using a hot air oven, wherein the drying temperature was 80° C., the drying time was 5 minutes, and the thickness of the photosensitive resin composition layer after drying was 29 ⁇ m.
  • a dry film photoresist was prepared by lamination using a protective film (polyethylene) on the dried photosensitive resin composition layer.
  • Fine wire adhesion (unit: ⁇ m)
  • Dry film photoresist laminated on RTF (Reverse Treated Foil) is used with ORC FDi-3 (Laser Direct Image exposure machine) at an exposure dose of 19mJ/cm 2 for fine wire adhesion patterns (from 10 ⁇ m to 58 ⁇ m, the width increases by 2 ⁇ m) and an array having a pattern interval of 400 ⁇ m) was irradiated with ultraviolet rays and left for 15 minutes.
  • the PET film which is the support of the dry film photoresist, was peeled off, and development was performed for 40 seconds under spray pressure of 1.5 kgf/cm 2 with a 1.0 wt% aqueous solution of Na 2 CO 3 at 30 ⁇ 1° C. under spray-type development conditions.
  • the minimum line width of the photosensitive resin layer was measured with a ZEISS AXIOPHOT Microscope, and the fine wire adhesion was evaluated. It can be evaluated that the fine wire adhesion is excellent, so that this value is small.
  • Dry film photoresist laminated on RTF (Reverse Treated Foil) is used with ORC FDi-3 (Laser Direct Image exposure machine) with an exposure amount of 19mJ/cm 2 and the resolution pattern (width increases by 2 ⁇ m from 10 ⁇ m to 58 ⁇ m) array with a pattern interval of 400 ⁇ m) was irradiated with UV light and left for 15 minutes.
  • the PET film which is the support of the dry film photoresist, was peeled off, and development was performed for 40 seconds under spray pressure of 1.5 kgf/cm 2 with a 1.0 wt% aqueous solution of Na 2 CO 3 at 30 ⁇ 1° C. under spray-type development conditions.
  • the minimum value of the gap between the photosensitive resin layers was measured with a ZEISS AXIOPHOT Microscope to evaluate the resolution. It can be evaluated that the resolution value is excellent, so that this value is small.
  • Dry film photoresist laminated on RTF Reverse Treated Foil
  • RTF Reverse Treated Foil
  • ORC FDi-3 Laser Direct Image exposure machine
  • the PET film which is the support of the dry film photoresist
  • the photocured film is developed for 40 seconds with a spray pressure of 1.5kgf/cm2 at a spray pressure of 1.5kgf/cm2 with an aqueous solution of Na 2 CO 3 at 30 ⁇ 1 °C. prepared.
  • peeling was performed using a 3% aqueous sodium hydroxide solution (temperature of 50° C.).
  • a 3% aqueous sodium hydroxide solution temperature of 50° C.
  • the Matte side of the Reverse Treated Foil having a thickness of 1.0mm and a surface roughness of about 5 ⁇ m in which the photosensitive resin layer of the dry film photoresist was soft-etched by peeling off the protective film of the dry film photoresist prepared in Examples and Comparative Examples
  • a laminate was formed by lamination using a HAKUTO MACH 610i under the conditions of a laminator roll temperature of 110° C., a roll pressure of 4.0 kgf/cm 2 , and a roll speed of 2.0 min/m so as to be in contact with the surface.
  • 3M #610 Tape which is a standard tape
  • 3M #610 Tape is adhered to the photosensitive resin layer
  • 3M #610 Tape is applied using a SurTA peel tester (ChemiLab). The tape peeling test was performed to evaluate the RTF adhesion, and is shown in Table 2 below.
  • the RTF adhesion is the percentage ratio of the surface area of the photosensitive resin layer of the dry film photoresist in contact with the substrate after the tape peeling test compared to the surface area of the photosensitive resin layer of the dry film photoresist in contact with the substrate before the tape peeling test as shown in Equation 1 below. do.
  • Adhesion (%) (Surface area of the substrate and photosensitive resin layer after the tape peeling test / Surface area of the photosensitive resin layer in contact with the substrate before the tape peeling test) * 100.
  • Example 2 As shown in Table 2, it was confirmed that the Example exhibited excellent fine wire adhesion and resolution, and remarkably exhibited RTF adhesion. Unlike the examples, in Comparative Example 1 not including the monofunctional (meth)acrylate compound, it was confirmed that the RTF adhesion was significantly inferior to that of the present Example. In addition, the polyfunctional (meth)acrylate compound In the case of Comparative Example 2, which does not include, it was confirmed that the fine wire adhesion and resolution were significantly inferior to those of the present Example.

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  • General Physics & Mathematics (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials For Photolithography (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

La présente invention concerne une composition de résine photosensible, qui comprend un composé photopolymérisable monofonctionnel et un composé photopolymérisable polyfonctionnel ayant trois groupes fonctionnels ou plus et présente une excellente adhérence à un substrat, et un film photosensible sec et un élément photosensible qui utilisent cette composition.
PCT/KR2020/018172 2019-12-31 2020-12-11 Couche de résine photosensible, et film photosensible sec et élément photosensible l'utilisant WO2021137468A1 (fr)

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JP2022538988A JP7509885B2 (ja) 2019-12-31 2020-12-11 感光性樹脂層、それを用いたドライフィルムフォトレジスト、および感光性エレメント
CN202080088795.XA CN114902133A (zh) 2019-12-31 2020-12-11 光敏树脂层和使用该光敏树脂层的干膜光刻胶、光敏元件

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KR10-2020-0095387 2019-12-31
KR10-2019-0179945 2019-12-31
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KR102177313B1 (ko) * 2019-12-31 2020-11-16 코오롱인더스트리 주식회사 감광성 수지 조성물 및 이를 이용한 드라이 필름 포토레지스트, 감광성 엘리먼트, 회로기판, 및 디스플레이 장치

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JPH11316456A (ja) * 1998-02-17 1999-11-16 Toppan Printing Co Ltd 無溶剤型感光性焼成ペ―スト組成物及び溶剤型感光性焼成ペ―スト組成物および構造体
US20090263746A1 (en) * 2008-04-17 2009-10-22 Ray Kevin B Method of making lithographic printing plates with simple processing
KR20130004110A (ko) * 2011-06-29 2013-01-09 토요켐주식회사 감광성 수지 조성물 및 그의 경화물, 그리고 감광성 솔더 레지스트 잉크, 드라이 필름형 감광성 솔더 레지스트 및, 감광성 수지의 제조 방법
JP2013037272A (ja) * 2011-08-10 2013-02-21 Mitsubishi Paper Mills Ltd 感光性樹脂組成物及び感光性フィルム
JP2014114386A (ja) * 2012-12-10 2014-06-26 Sanyo Chem Ind Ltd 感光性組成物及び硬化物
KR20160038358A (ko) * 2014-09-30 2016-04-07 코오롱인더스트리 주식회사 드라이 필름 포토 레지스트용 감광성 수지 조성물
KR102177313B1 (ko) * 2019-12-31 2020-11-16 코오롱인더스트리 주식회사 감광성 수지 조성물 및 이를 이용한 드라이 필름 포토레지스트, 감광성 엘리먼트, 회로기판, 및 디스플레이 장치

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