WO2023043041A1 - Composition de résine photosensible - Google Patents

Composition de résine photosensible Download PDF

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Publication number
WO2023043041A1
WO2023043041A1 PCT/KR2022/010830 KR2022010830W WO2023043041A1 WO 2023043041 A1 WO2023043041 A1 WO 2023043041A1 KR 2022010830 W KR2022010830 W KR 2022010830W WO 2023043041 A1 WO2023043041 A1 WO 2023043041A1
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WO
WIPO (PCT)
Prior art keywords
photosensitive resin
resin composition
weight
epoxy resin
group
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PCT/KR2022/010830
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English (en)
Korean (ko)
Inventor
김창혁
홍승민
하명식
최형욱
Original Assignee
주식회사 케이씨씨
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Publication of WO2023043041A1 publication Critical patent/WO2023043041A1/fr

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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
    • C08F2/46—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
    • 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
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

Definitions

  • the present invention relates to a photosensitive resin composition having excellent developability and deep curing properties.
  • the photosensitive resin composition can form fine patterns by applying the principle of photolithography, it is used in various forms to form fine circuit patterns on electronic devices or printed circuit boards.
  • These photosensitive resin compositions have a solvent developing type and an alkali developing type.
  • the amount of alkali developing photosensitive resin compositions that can be developed using a weak alkaline aqueous solution is increasing in order to reduce the amount of solvent used. .
  • an alkali developable photosensitive resin composition is variously used in manufacturing printed wiring boards, manufacturing liquid crystal display panels, or printing plate making.
  • the photosensitive resin composition can be used as a solder resist (SR) that protects a portion of the board that is not to be touched with lead during soldering during manufacturing of the printed wiring board.
  • SR solder resist
  • Solder resist is a protective material on the printed circuit board, which prevents solder from adhering to unnecessary parts (non-leaded parts, parts requiring insulation) when solder is formed on the board, and can withstand high temperature conditions such as soldering so that solder bridges are not formed. At the same time, it must have heat resistance and be able to maintain the electrical insulation of the conductive part.
  • solder resist compositions have heat resistance, In addition to insulating properties, physical properties for inhibiting crack generation during cooling and heating cycles are also required.
  • Patent No. 10-1,063,048 discloses an alkali developable solder resist including a carboxyl group-containing photosensitive resin, an oxime ester-based photopolymerization initiator, an ethylenically unsaturated group-containing compound, and a thermosetting component.
  • an alkali developable solder resist including a carboxyl group-containing photosensitive resin, an oxime ester-based photopolymerization initiator, an ethylenically unsaturated group-containing compound, and a thermosetting component.
  • the present invention provides a liquid type photosensitive resin composition having excellent developability and deep curing properties.
  • the present invention provides a liquid photosensitive resin composition
  • a liquid photosensitive resin composition comprising a photosensitive resin having a urethane group, an epoxy resin, and a photoinitiator.
  • the present invention provides a liquid type photosensitive resin composition having excellent developability and deep curing properties.
  • the photosensitive resin composition of the present invention uses a photosensitive resin having a urethane group having an equivalent of a urethane acrylate group in a specific range, and since a photocuring reaction occurs effectively even with weak light reaching the depths, the solder resist formed of the composition The undercut is improved as the core hardening is improved, and it has excellent reliability.
  • the functional value such as "acid value” used herein, is measured by a conventional method known in the art, and can be measured, for example, by a titration method.
  • Weight average molecular weight is measured by a conventional method known in the art, and can be measured, for example, by a gel permeation chromatograph (GPC) method.
  • Softening point is measured by a conventional method known in the art. It can be measured with, for example, a Dropping Point system calorimetry DP70 from Mettler Toledo.
  • the liquid photosensitive resin composition according to the present invention includes a photosensitive resin having a urethane group, an epoxy resin, and a photoinitiator.
  • the liquid photosensitive resin composition according to the present invention may include an acrylic monomer and a solvent, and may further include additives commonly used in the art, such as catalysts, ion catchers, fillers, and pigments, if necessary.
  • Photosensitive resin having a urethane group
  • the liquid type photosensitive resin composition of the present invention includes a photosensitive resin having a urethane group (-NH-COO-).
  • the photosensitive resin having a urethane group imparts photocurability that cures in response to light and developability capable of forming a pattern to the photosensitive resin composition.
  • a photosensitive resin having a urethane group including a urethane acrylate group as a photosensitive group that reacts to light, excellent deep curing characteristics are imparted to the photosensitive resin composition, and as a result, improved developability and resolution are exhibited.
  • the photosensitive resin having a urethane group of the present invention serves to improve physical properties such as UV curability, adhesion, elasticity, and chemical resistance of the photosensitive resin composition.
  • the photosensitive resin having a urethane group may be prepared by a manufacturing method including a step of preparing a polyol from a phenolic resin, an addition reaction step of an acrylate having an isocyanate group, and an acid modification step.
  • alkylene oxide or alkylene carbonate is reacted with a phenolic resin such as phenol, cresol or a novolak resin of a derivative thereof, and a (meth)acrylic monomer having an isocyanate group is reacted with the polyol produced by the reaction, It can be prepared by reacting a compound having an acid anhydride group with the remaining hydroxyl group.
  • a phenolic resin such as phenol, cresol or a novolak resin of a derivative thereof
  • a (meth)acrylic monomer having an isocyanate group is reacted with the polyol produced by the reaction, It can be prepared by reacting a compound having an acid anhydride group with the remaining hydroxyl group.
  • Non-limiting examples of the alkylene oxide include ethylene oxide, propylene oxide, and the like, which may be used alone or in combination.
  • Non-limiting examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, and the like, which may be used alone or in combination.
  • Non-limiting examples of the (meth)acrylic monomer having an isocyanate group include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and the like, and these may be used alone or in combination.
  • Non-limiting examples of the compound having the acid anhydride group include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl-hexahydrophthalic anhydride, phthalic anhydride, and the like, which are alone or may be used in combination.
  • the photosensitive resin having a urethane group may include a repeating unit represented by Formula 1 below; And a repeating unit represented by the following formula (2) and a repeating unit represented by the following formula (3) It may contain one or more repeating units.
  • R 1 and R 2 is hydrogen or an alkyl group having 1 to 5 carbon atoms
  • R 3 is an alkyl group having 1 to 10 carbon atoms, an aliphatic alkylene having 2 to 9 carbon atoms, a cyclic alkylene, or an aromatic divalent compound.
  • the photosensitive resin having a urethane group may include a repeating unit represented by Chemical Formula 1 and a repeating unit represented by Chemical Formula 2.
  • the photosensitive resin having a urethane group may include a repeating unit represented by Chemical Formula 1, a repeating unit represented by Chemical Formula 2, and a repeating unit represented by Chemical Formula 3.
  • the photosensitive resin having a urethane group may include 2 to 50 repeating units represented by Chemical Formula 1 and 2 to 50 repeating units represented by Chemical Formula 2.
  • the photosensitive resin having a urethane group includes 2 to 50 repeating units represented by Formula 1, includes 2 to 50 repeating units represented by Formula 2, and repeats units represented by Formula 3 Can contain 5 or less.
  • the equivalent of the urethane acrylate group of the photosensitive resin having a urethane group may be 260 to 700 g/eq, for example, 300 to 600 g/eq.
  • the equivalent weight of the urethane acrylate group in the photosensitive resin having a urethane group is within the above-mentioned range, curing occurs effectively not only on the surface of the coating film but also in the light reaching the deep part, so that excellent pattern forming properties can be exhibited.
  • the equivalent weight of the urethane acrylate group is less than the above-mentioned range, the number of crosslinkable acrylates in response to light is too large, so that the curing density is excessively increased, thereby lowering the developability with respect to an alkali developer and leaving residues on the substrate.
  • the equivalent weight of the urethane acrylate group of the photosensitive resin having a urethane group exceeds the above range, the number of crosslinkable acrylates in response to light is too small, resulting in a significant decrease in curing density, resulting in a need not to be developed.
  • the cured coating film portion (the portion where the pattern is to be formed) is etched (etched) by the developing solution and the pattern is lost, so that desired pattern and resolution cannot be obtained, and physical properties of the cured coating film may be deteriorated.
  • the acid value of the photosensitive resin having a urethane group may be 40 to 120 mgKOH/g, for example, 50 to 100 mgKOH/g. If the acid value is less than the above range, developability with an alkali developer may be lowered and residues may be left on the substrate, and if the acid value exceeds the above range, the pattern may be detached.
  • the weight average molecular weight of the photosensitive resin having a urethane group may be 2,000 to 20,000 g/mol, for example, 2,000 to 10,000 g/mol. If the weight average molecular weight is less than the above-mentioned range, the binding between the components in the composition required as a binder resin, that is, the binding function is weakened, and as a result, the shape of the pattern may be lost or crushed because it cannot withstand the physical external force during development, heat resistance, content Jeseong, etc. may be inferior. On the other hand, when the weight average molecular weight exceeds the above-mentioned range, developability with respect to an alkaline developer is poor and flowability is deteriorated, making it difficult to control the thickness of the coating film or to secure uniformity.
  • the liquid photosensitive resin composition of the present invention may include 25 to 55% by weight, for example, 30 to 50% by weight of the photosensitive resin having a urethane group, based on the total weight of the liquid photosensitive resin composition.
  • content of the photosensitive resin is less than the above range, physical properties such as heat resistance and solvent resistance may be deteriorated, and when it exceeds the above range, storage stability and flowability may be deteriorated, resulting in deterioration in workability.
  • the liquid type photosensitive resin composition according to the present invention includes an epoxy resin.
  • the epoxy resin imparts thermosetting properties in which the photosensitive resin composition can be cured by reacting with heat.
  • polyglycidyl ethers of polyhydric phenols and derivatives thereof may be used.
  • bisphenol A type epoxy resins which are polyglycidyl ethers of polyhydric phenols, hydrogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolac epoxy resins, phenol-novolac epoxy resins, cresol-novolac epoxy resins , N-glycidyl epoxy resin, bisphenol A novolac epoxy resin, chelate type epoxy resin, glyoxane epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenolic epoxy resin, silicon-modified epoxy resin , ⁇ -caprolactone-modified epoxy resins, bisphenol S epoxy resins, diglycidyl phthalate resins, heterocyclic epoxy resins, biphenyl epoxy resins and the like can be used.
  • the epoxy resin includes a bisphenol-type epoxy resin, a biphenyl epoxy resin, or a mixture thereof.
  • the two types of epoxy resins are used together, excellent adhesion and chemical resistance can be obtained from the bisphenol-type epoxy resin, and heat resistance and thermal stability under heat drying conditions can be supplemented from the biphenyl epoxy resin.
  • the bisphenol-type epoxy resin has an epoxy equivalent of 200 to 600 g/eq, for example 400 to 500 g/eq, a softening point of 50 to 100 °C, for example 60 to 70 °C, and a weight average molecular weight of 1,000 to 1,000 5,000 g/mol, for example 1,500 to 2,500 g/mol may be used.
  • an epoxy equivalent of 200 to 600 g/eq for example 400 to 500 g/eq
  • a softening point of 50 to 100 °C, for example 60 to 70 °C
  • a weight average molecular weight 1,000 to 1,000 5,000 g/mol, for example 1,500 to 2,500 g/mol
  • the bisphenol-type epoxy resin may be a bisphenol A-type epoxy resin represented by Formula 4 below.
  • the biphenyl epoxy resin has an epoxy equivalent of 100 to 1,000 g/eq, for example, 350 to 600 g/eq, and a weight average molecular weight of 300 to 20,000 g/mol, for example, 1,000 to 3,000 g/mol. can be used When the physical properties of the biphenyl epoxy resin satisfy the aforementioned range, excellent heat resistance and thermal stability may be exhibited.
  • biphenyl epoxy resin examples include aliphatic epoxy resins, fatty acid-based epoxy resins derived from natural products, polybutadiene-based epoxy resins, and cycloaliphatic epoxy resins.
  • the liquid photosensitive resin composition of the present invention may include 6 to 40% by weight, for example, 10 to 30% by weight of the epoxy resin based on the total weight of the liquid photosensitive resin composition. For example, based on the total weight of the liquid photosensitive resin composition, 3 to 20% by weight of the bisphenol A epoxy resin, for example 5 to 15% by weight and 3 to 20% by weight of the biphenyl epoxy resin, for example 5 to 15% by weight 15% by weight.
  • the content of each epoxy resin is less than the above range, the curing promoting effect may be insufficient, and when it exceeds the above range, the appearance of the coating may be poor or the strength of the coating film may be weakened.
  • the liquid photosensitive resin composition of the present invention includes a photoinitiator.
  • a photoinitiator a benzophenone-based compound, a benzoin alkyl ether-based compound, an acetophenone-based compound, a thioxanthone-based compound, an alkylanthraquinone-based compound, and an acylphosphine oxide-based compound may be used.
  • the photoinitiator may include two or more types of photoinitiators having different effective absorption wavelengths.
  • the photoinitiators having different effective absorption wavelengths can sufficiently advance curing in the surface and core of the coating film, respectively.
  • the undercut phenomenon is reduced during development with an alkaline developer after curing, so that resolution is improved and excellent fine pattern formability can be secured.
  • at least one first photoinitiator having an effective absorption wavelength of 250 to 320 nm and at least one second photoinitiator having an effective absorption wavelength of 370 to 450 nm may be included.
  • the first photoinitiator is an ⁇ -amino acetophenone-based compound, for example, 2-benzyl-2-dimethylamino-1-(4-morpholino-phenyl)-1-butanone (2-Benzyl-2 -dimethylamino-1-(4-morpholino-phenyl)-1-butanone), 2-methyl-1-[(4-methylthio)phenyl]-2-(4-morpholinyl)-1-propanol, 2-( 4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one or a mixture thereof.
  • 2-benzyl-2-dimethylamino-1-(4-morpholino-phenyl)-1-butanone (2-Benzyl-2 -dimethylamino-1-(4-morpholino-phenyl)-1-butanone
  • the second photoinitiator is a thioxanthone-based compound, for example, 2,4-diethylthioxanthone (2,4-diethylthioxanthone), 2,4-dimethylthioxanthone, 2,4-diisopropyl tea oxanthone, 2-chlorothioxanthone or a mixture thereof.
  • the mixing ratio (weight ratio) of the first photoinitiator and the second photoinitiator may be 7:3 to 9:1, for example, 7:3 to 8:2.
  • the mixing ratio of the first photoinitiator exceeds the above range and is mixed in an excessive amount, surface hardening may occur excessively and deep hardening may become weak.
  • the mixing ratio of the second photoinitiator exceeds the above-mentioned range and is mixed in an excessive amount, surface hardening may be weakened and storage stability may be deteriorated.
  • the liquid photosensitive resin composition of the present invention may include 1.1 to 15% by weight, for example, 1.1 to 6% by weight of the photoinitiator based on the total weight of the liquid photosensitive resin composition.
  • the radical initiation reaction may not occur smoothly, and when it exceeds the above range, the reaction rate between the radical and the double bond of the photoinitiator is too fast, making it difficult to form a high molecular weight.
  • 1 to 10% by weight, for example, 1 to 5% by weight of the first photoinitiator and 0.1 to 5% by weight, for example, 0.1 to 1% by weight of the second photoinitiator can include
  • the liquid photosensitive resin composition according to the present invention may contain an acrylic monomer.
  • the acrylic monomer serves to impart photocurability.
  • the acrylic monomer may be a multifunctional acrylic monomer, for example, a trifunctional or higher functional (meth)acrylate monomer, for example, a trifunctional to hexafunctional.
  • Non-limiting examples of the multifunctional acrylic monomer include trifunctional (meth)acrylate monomers such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate; tetrafunctional (meth)acrylate monomers such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate; There are dipentaerythritol poly(meth)acrylates such as dipentaerythritol hexa(meth)acrylate and the like, which may be used alone or in combination of two or more.
  • the liquid photosensitive resin composition of the present invention may include 3 to 30% by weight, for example, 5 to 20% by weight of the acrylic monomer based on the total weight of the liquid photosensitive resin composition. If the content of the acrylic monomer is less than the above range, photocurability is not sufficient, and pattern formation by alkali development after light irradiation may be difficult. The solubility of the photosensitive resin composition for the film may be weakened.
  • the liquid photosensitive resin composition according to the present invention may further contain an organic solvent and other additives, if necessary, within a range that does not degrade physical properties of the liquid photosensitive resin composition of the present invention.
  • the organic solvent is for adjusting the viscosity and is not particularly limited as long as it is used in the related art.
  • dipropylene glycol monoethyl ether, naphtha, and the like may be used.
  • additives commonly used in the art such as catalysts, ion catchers, fillers, and pigments, may be used.
  • the catalyst is for accelerating the thermal curing reaction, and is not particularly limited as long as it is used in the related art.
  • melamine or the like may be used.
  • the ion catcher is for removing eluting ions, and is not particularly limited as long as it is used in the related art.
  • Al, Mg, and Zr-based inorganic materials may be used.
  • the filler is not particularly limited as long as it is used in the art as a filler, and inorganic fillers such as barium sulfate, talc, silica, aluminum oxide, and aluminum hydroxide may be used.
  • barium sulfate having a particle size (D50) of 20 ⁇ m or less, for example, 10 ⁇ m or less, and another example of 1 ⁇ m or less may be used.
  • the pigment is for imparting a coloring effect, and is not particularly limited as long as it is used in the related art.
  • azo-based pigments, phthalocyanine-based pigments, and the like may be used.
  • finely divided silica for imparting thixotropy a dispersing agent for helping to disperse the filler, and an antifoaming agent for forming a smooth coating film surface may be included.
  • the photosensitive resin composition of the present invention is in liquid form and can be used as a photosensitive composition for a printed circuit board requiring a fine image or a photosensitive composition for a printed circuit board requiring a negative image.
  • a pattern may be formed by directly applying the photosensitive resin composition of the present invention in liquid form to a substrate.
  • the base material include printed wiring boards or flexible printed wiring boards with pre-circuits, glass fibers impregnated with phenol resin, glass fibers impregnated with epoxy resin, glass fibers impregnated with bismaleimide triazine resin, copper clad laminates, and polyimide films.
  • PET film, glass substrates, ceramic substrates, wafer substrates and the like can be used.
  • a dip coating method, a flow coating method, a roll coating method, a bar coating method, a screen printing method, a curtain coating method, etc. and volatilize and dry the organic solvent contained in the composition at a temperature of about 60 to 120 ° C.
  • a hot air circulation drying furnace, an infrared drying furnace, a hot plate, or the like can be used.
  • the exposure machine used for active energy irradiation includes a direct writing device (e.g., a laser direct image device that directly expresses a pattern with a laser using CAD data on a computer), an exposure machine equipped with a metal halide lamp, and a (ultra)high pressure mercury lamp.
  • a direct writing device e.g., a laser direct image device that directly expresses a pattern with a laser using CAD data on a computer
  • an exposure machine equipped with a metal halide lamp e.g., a laser direct image device that directly expresses a pattern with a laser using CAD data on a computer
  • a direct drawing device using an ultraviolet lamp such as a (ultra)high pressure mercury lamp, or the like can be used.
  • the active energy laser light and ultraviolet lamp light having a maximum wavelength of 340 to 420 nm may be used, and both gas lasers and solid-state lasers may be used.
  • a pattern may be formed by selectively exposing with active energy through
  • a dipping method, a shower method, a spray method, a brush method, etc. may be used.
  • an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, or amines may be used.
  • a pattern may be formed by developing with an alkaline aqueous solution (0.1-3.0% sodium carbonate aqueous solution).
  • the photosensitive resin composition of the present invention includes an epoxy resin having a thermosetting property, and when heated at a temperature of 130 to 160 ° C., a carboxyl group of a highly heat-resistant resin containing an unsaturated double bond and a carboxyl group and two or more rings in the molecule
  • a thermosetting component having a type (thio)ether group reacts to form a cured film having excellent heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics.
  • a printed wiring board including a solder resist obtained by using the photosensitive resin composition, a patterned cured product of the photosensitive resin composition, and a patterned cured product layer of the photosensitive resin composition can be provided. there is.
  • Photosensitive resin 3 having a urethane group (solid content 64%, urethane acrylate group equivalent weight 250 eq/g, acid value 35 mgKOH/g, weight average molecular weight 3,900 g/mol) were synthesized.
  • Photosensitive resin 4 having a urethane group (solid content 64.4%, urethane acrylate group equivalent weight 830 eq/g, acid value 128 mgKOH/g, weight average molecular weight 4,120 g/mol) was synthesized.
  • the photosensitive resin composition of each experimental example was prepared by mixing each component according to the composition shown in Table 1 below.
  • Photosensitive resin 1 Photosensitive resin 1 having a urethane group of Synthesis Example 1 (solid content 64%, urethane acrylate group equivalent 377 eq/g, acid value 73 mgKOH/g, weight average molecular weight 4,100 g/mol)
  • Photosensitive resin 2 Photosensitive resin 2 having a urethane group of Synthesis Example 2 (solid content 62%, urethane acrylate group equivalent 536 eq/g, acid value 66 mgKOH/g, weight average molecular weight 4,010 g/mol)
  • Photosensitive resin 3 Photosensitive resin 3 having a urethane group of Synthesis Example 3 (solid content 64%, urethane acrylate group equivalent 250 eq/g, acid value 35 mgKOH/g, weight average molecular weight 3,900 g/mol)
  • Photosensitive resin 4 Photosensitive resin 4 having a urethane group of Synthesis Example 4 (solid content 64.4%, urethane acrylate group equivalent 830 eq/g, acid value 128 mgKOH/g, weight average molecular weight 4,120 g/mol)
  • Photosensitive resin 5 acid modified epoxy acrylate (Epoxy acrylate modified with THFA, acid value 52-56 mgKOH/g, Mw: 7,500 g/mol)
  • Epoxy resin 1 bisphenol A type epoxy resin (EEW 450 g/eq, Mw 2,000 g/mol)
  • Epoxy Resin 2 Biphenyl Epoxy Resin (EEW 180 g/eq, Mw 354 g/mol)
  • Acrylic monomer DPHA (Dipentaerythritol hexaacrylate, hexafunctional)
  • Photoinitiator 1 2-Benzyl-2-dimethylamino-1-(4-morpholino-phenyl)-1-butanone (effective absorption wavelength 250-315 nm)
  • Photoinitiator 2 2,4-diethylthioxanthone (DETX) (effective absorption wavelength 375-450 nm)
  • Ion catcher mixture of 70% Mg 6 Al 2 [(OH) 16 CO 3 ]*4H 2 O and 30% Zr(HPO 4 ) 2
  • Pigment 1 azo pigment
  • Pigment 2 phthalocyanine-based pigment
  • Solvent 1 Dipropylene glycol monomethyl ether
  • the resin composition of each experimental example was applied on a substrate by a screen printing method, dried at 80 DEG C for 30 minutes, and cooled at room temperature.
  • a 41-stage step tablet for sensitivity evaluation was pressed on the dried coating layer, exposed to 700 mJ/cm 2 through an exposure machine equipped with a high-pressure mercury lamp, developed for 90 seconds with a 1% sodium carbonate aqueous solution at 30 ° C, and washed with water. After that, the sensitivity was evaluated by observing the largest stage in the glossy stage.
  • the resin composition of each experimental example was applied on a substrate by a screen printing method, taken out at 80°C from 30 minutes to 100 minutes at intervals of 10 minutes, and cooled at room temperature. Thereafter, it was developed for 120 seconds with a 1% sodium carbonate aqueous solution at 30° C., and the maximum allowable drying time (development margin) at which no residue was left was measured.
  • the resin composition of each experimental example was applied on a substrate by a screen printing method, dried at 80 DEG C for 30 minutes, and cooled at room temperature. After pressing the film for pattern mask on the substrate prepared as described above and exposing at 700 mJ / cm 2 through an exposure machine equipped with a high-pressure mercury lamp, developing for 90 seconds with a 1% sodium carbonate aqueous solution at 30 ° C. and washing with water to form a pattern . The minimum opening size (resolvability) maintaining the shape of a circle was measured.
  • the resin composition of each experimental example was applied on a substrate by a screen printing method, dried at 80 DEG C for 30 minutes, and cooled at room temperature.
  • the peak area (a) at the acrylic characteristic peak (1,410 cm -1 ) was measured through FT-IR analysis of the dried specimen.
  • the dried coating layer was exposed to 700 mJ/cm 2 through an exposure machine equipped with a high pressure mercury lamp, and thermally cured using a hot air oven at 150° C. for 1 hour, and then additionally exposed to 1,200 mJ/cm 2 through an exposure machine equipped with a high pressure mercury lamp. After polishing the surface of the final cured specimen to reduce the thickness of the coating layer, the peak area (b) of the acrylic characteristic peak was measured through FT-IR analysis.
  • Acrylic curing degree (deep curing property) was evaluated by the following formula.
  • the resin composition of each experimental example was applied on a substrate by a screen printing method, dried at 80 DEG C for 30 minutes, and cooled at room temperature. After pressing the film for pattern mask on which the SR Dam (width 100 um) is formed on the dried substrate, exposing at 700 mJ/cm2 through an exposure machine equipped with a high-pressure mercury lamp, developing for 90 seconds in 1% sodium carbonate aqueous solution at 30 ° C. and washed up. Thereafter, after thermal curing through a 150 ° C. hot air oven for 1 hour, 1,200 mJ/cm 2 additional exposure was performed through an exposure machine equipped with a high-pressure mercury lamp.
  • the substrate manufactured by the above method was cut with scissors at the part where the SR Dam (width: 100 um) was formed, molded with a molding solution, polished the cross section of the Dam, and then used a microscope (X 500 magnification) for a total of 10 times. The undercut was measured and the average value was recorded.
  • the resin composition of each experimental example was applied on a substrate by a screen printing method, dried at 80 DEG C for 30 minutes, and cooled at room temperature.
  • a film for pattern mask is pressed on the dried substrate, exposed to 700 mJ/cm2 through an exposure machine equipped with a high-pressure mercury lamp, and thermally cured through a hot air oven at 150 ° C for 1 hour, and then through an exposure machine equipped with a high-pressure mercury lamp. 1,200 mJ/cm 2 was additionally exposed.
  • the substrate manufactured by the above method was immersed in a soldering bath set at 260 DEG C for 10 seconds. After repeating the immersion process three times, changes in the appearance of the SR layer and peeling were observed with the naked eye.
  • the resin composition of each experimental example was applied on a substrate by a screen printing method, dried at 80 DEG C for 30 minutes, and cooled at room temperature.
  • the dried substrate was exposed to 700 mJ/cm 2 through an exposure machine equipped with a high-pressure mercury lamp, and thermally cured in a 150° C. hot air oven for 1 hour, followed by additional exposure of 1,200 mJ/cm 2 through an exposure machine equipped with a high-pressure mercury lamp.
  • the resin composition of each experimental example was applied to a BT substrate on which electrodes (line space: 30 ⁇ m) were formed by screen printing, dried at 80° C. for 30 minutes, and then cooled at room temperature.
  • the dried substrate was exposed to 700 mJ/cm 2 through an exposure machine equipped with a high-pressure mercury lamp, and thermally cured in a 150° C. hot air oven for 1 hour, followed by additional exposure of 1,200 mJ/cm 2 through an exposure machine equipped with a high-pressure mercury lamp.
  • a voltage of 5V was applied to the substrate manufactured by the above method under high temperature and high humidity conditions of 130 ° C. and 85% humidity, and HAST evaluation was performed for 168 hours. After 168 hours, the insulation resistance value was measured.
  • the photosensitive resin compositions of Experimental Examples 1-4 using the photosensitive resin having a urethane group according to the present invention exhibited excellent physical properties in all measurement items.
  • the present invention provides a liquid type photosensitive resin composition having excellent developability and deep curing properties.
  • the photosensitive resin composition of the present invention uses a photosensitive resin having a urethane group having an equivalent of a urethane acrylate group in a specific range, and since a photocuring reaction occurs effectively even with weak light reaching the depths, the solder resist formed of the composition The undercut is improved as the core hardening is improved, and it has excellent reliability.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne une composition de résine photosensible en phase liquide ayant une excellente aptitude au développement et une excellente aptitude au durcissement de partie profonde.
PCT/KR2022/010830 2021-09-14 2022-07-22 Composition de résine photosensible WO2023043041A1 (fr)

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KR1020210122416A KR102673184B1 (ko) 2021-09-14 2021-09-14 감광성 수지 조성물
KR10-2021-0122416 2021-09-14

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JP6201325B2 (ja) 2012-02-29 2017-09-27 東洋インキＳｃホールディングス株式会社 キノフタロン色素単量体、およびそれを用いた着色性ポリマー、およびそれを用いた着色感光性組成物、およびその用途
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JPH05239426A (ja) * 1992-03-03 1993-09-17 Yokohama Rubber Co Ltd:The 接着剤組成物
KR20030097780A (ko) * 2001-07-04 2003-12-31 쇼와 덴코 가부시키가이샤 레지스트 경화성 수지 조성물 및 그 경화물
KR20100002574A (ko) * 2008-06-30 2010-01-07 주식회사 코오롱 포토레지스트 조성물, 드라이 필름 포토레지스트, 부조상패턴, 패턴 형성방법 및 전자부품
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