WO2021036527A1 - 树脂组合物及其应用 - Google Patents

树脂组合物及其应用 Download PDF

Info

Publication number
WO2021036527A1
WO2021036527A1 PCT/CN2020/100911 CN2020100911W WO2021036527A1 WO 2021036527 A1 WO2021036527 A1 WO 2021036527A1 CN 2020100911 W CN2020100911 W CN 2020100911W WO 2021036527 A1 WO2021036527 A1 WO 2021036527A1
Authority
WO
WIPO (PCT)
Prior art keywords
epoxy resin
resin
parts
resin composition
type epoxy
Prior art date
Application number
PCT/CN2020/100911
Other languages
English (en)
French (fr)
Inventor
林晓英
童荣柏
李伟杰
钱伟强
周光大
林建华
Original Assignee
浙江福斯特新材料研究院有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 浙江福斯特新材料研究院有限公司 filed Critical 浙江福斯特新材料研究院有限公司
Priority to EP20856582.0A priority Critical patent/EP4024134A4/en
Priority to US17/638,204 priority patent/US20220308450A1/en
Publication of WO2021036527A1 publication Critical patent/WO2021036527A1/zh

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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
    • G03F7/027—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
    • G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0385—Macromolecular compounds which are rendered insoluble or differentially wettable using epoxidised novolak resin
    • 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
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/322—Aqueous alkaline compositions
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions
    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0213—Electrical arrangements not otherwise provided for
    • H05K1/0237—High frequency adaptations
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide

Definitions

  • the present invention relates to the technical field of circuit board printing, in particular to a resin composition and its application, and in particular to a resin composition for high-frequency and high-speed printed circuit boards.
  • PCB and FPCB materials are required to reduce electrical signal loss in the high-frequency region, specifically the region with a frequency above 1GHz, which requires PCB and FPCB materials have low dielectric constant (Dk) and dielectric loss (Df). Among them, Dk should be less than or equal to 3.0, and Df should be less than or equal to 0.008.
  • the photosensitive polyimide cover film has a low Dk of 3.0 or less, but the Df is higher than 0.01.
  • the traditional PI cover film is composed of an epoxy adhesive layer and a polyimide resin layer, and the high polarity of the epoxy adhesive layer causes the Dk of the traditional CVL to be as high as 3.5 or more.
  • Existing solder mask inks, flexible inks and PIC photosensitive covering films all contain a large amount of highly polar epoxy resin and a higher concentration of polar groups, and the dielectric properties of the materials are also poor.
  • low dielectric constant and low dielectric loss photosensitive solder resist protective layer material such as cover film, solder resist ink or photosensitive cover film, etc.
  • low dielectric materials basically uses polytetrafluoroethylene resin, maleimide resin, thermosetting polyphenylene ether resin, cyanate resin, polyimide resin, and low dielectric epoxy resin. Resin and liquid crystal polymer; In the field of solder mask protective layer, there are few researches on low dielectric coating film, low dielectric resistance welding ink and low dielectric inductance optical coating film.
  • Chinese patent CN108287451A discloses a low dielectric inductance optical cover film resin composition.
  • the dielectric constant of the material is reduced by adding a fluorinated polymer to the epoxy acrylic resin system.
  • the fluorinated polymer has a particle size of 0.1-7 microns and is easy to Agglomeration and precipitation and poor compatibility with the host resin affect the overall dielectric and light transmittance of the material.
  • Chinese patent CN109923176A discloses a low-dielectric cover film for high-frequency signal transmission.
  • the main purpose of the present invention is to provide a resin composition and its application, so as to solve the problem that the resin composition in the prior art is not suitable for high-frequency and high-speed printing due to the lack of photosensitivity, dielectric properties, flexibility or processability.
  • the application problem in the circuit board is to provide a resin composition and its application, so as to solve the problem that the resin composition in the prior art is not suitable for high-frequency and high-speed printing due to the lack of photosensitivity, dielectric properties, flexibility or processability.
  • a resin composition comprising 100 parts by weight of alkali-soluble resin, 5-30 parts of acrylic monomers, 0.1 to 30 parts by weight. 10 parts of photoinitiator, 10-30 parts of the first epoxy resin and 0-15 parts of the second epoxy resin; wherein the first epoxy resin is a low-dielectric epoxy resin with a dielectric constant ⁇ 3.5.
  • the second epoxy resin is different from the first epoxy resin.
  • the low-dielectric epoxy resin is an epoxy resin containing at least two epoxy groups and an epoxy equivalent of 160-2000g/eq; preferably, the low-dielectric epoxy resin is a biphenyl type epoxy resin, naphthalene One of cyclic epoxy resins, naphthol epoxy resins, naphthylene ether epoxy resins, polyphenylene ether epoxy resins, dicyclopentadiene novolac epoxy resins, and crystalline fluorene epoxy resins One or more, more preferably naphthalene ring type epoxy resin.
  • biphenyl type epoxy resin has the structure shown in formula I:
  • n is a natural number from 1 to 10;
  • the naphthalene ring epoxy resin has the structure shown in formula II:
  • n is a natural number from 1 to 10;
  • the naphthol type epoxy resin has the structure shown in formula III:
  • n is a natural number from 1 to 10;
  • the naphthylene ether type epoxy resin has the structure shown in formula IV:
  • n is a natural number from 1 to 10;
  • Polyphenylene ether type epoxy resin has the structure shown in formula V:
  • x and y are natural numbers from 1 to 10 respectively;
  • Dicyclopentadiene type novolac epoxy resin has the structure shown in formula VI:
  • n is a natural number from 1 to 10;
  • the crystalline fluorene epoxy resin has the structure shown in formula VII:
  • the acid value of the alkali-soluble resin is 60-150 mg KOH/g; preferably, the alkali-soluble resin is selected from one or more of photosensitive epoxy acrylic resin, styrene acrylic resin, and photosensitive polyurethane acrylic resin; preferably Ground, the photosensitive epoxy acrylic resin is selected from carboxylic acid modified bisphenol A type epoxy resin, carboxylic acid modified bisphenol F type epoxy resin, carboxylic acid modified novolac epoxy resin, carboxylic acid modified o-cresol One or more of epoxy resins; preferably, the styrene-acrylic resin is selected from carboxylic acid-modified benzene acrylic resins with a weight average molecular weight of 3-20w and a glass transition temperature of 90-150°C; preferably, photosensitive polyurethane The acrylic resin is selected from one or more of aliphatic urethane acrylic resin, alicyclic urethane acrylic resin, and aromatic urethane acrylic resin.
  • the weight average molecular weight of the acrylate monomer is 200 to 2000, and the glass transition temperature is -20 to 100°C; preferably, the acrylate monomer is selected from (ethoxy) phenol (meth) acrylate , Stearic acid acrylate, ethoxy (propoxy) nonyl phenol (meth) acrylate, ethoxy (propoxy) tetrahydrofurfuryl (meth) acrylate, 1,6-hexanedi Alcohol diacrylate, PPG(400) diacrylate, tricyclodecane dimethanol diacrylate, dioxanediol diacrylate, ethoxylated (propoxylated) bisphenol A di(meth)acrylic acid Ester, polyethylene glycol (400) diacrylate, polypropylene glycol (600) diacrylate, ethoxy (propoxy) trimethylolpropane tri(meth)acrylate, pentaerythritol triacrylate, tri( One or
  • the photoinitiator includes a photopolymerization initiator and a photosensitizer, and the weight ratio of the photopolymerization initiator and the photosensitizer is 2-20:1; preferably, the photopolymerization initiator is selected from 1-hydroxycyclohexylphenylmethyl Ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-[4-(2-hydroxy)-phenyl]-3-hydroxy-2-methyl-1-propanone-1- Ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinebenzylbenzene) Yl) butanone, 2,4,6-trimethylbenzoyl-diphenylphosphorus oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6- One or more of ethyl trimethylbenzoylphenylphosphonate;
  • the resin composition further includes 3-10 parts of toughening resin; preferably, the toughening resin is selected from core-shell rubber toughened epoxy resin, thermoplastic elastomer, polyurethane elastomer, liquid rubber, One or more of rubber powder.
  • the toughening resin is selected from core-shell rubber toughened epoxy resin, thermoplastic elastomer, polyurethane elastomer, liquid rubber, One or more of rubber powder.
  • the resin composition further includes 0-5 parts of pigments and fillers and 0.01-5 parts of additives, and the additives are selected from one of thermal curing accelerators, dispersants, leveling agents, and defoamers Or more; preferably, the pigment and filler are selected from one or more of benzidine yellow, phthalocyanine green, phthalocyanine blue, carbon black, silicon dioxide, barium sulfate, calcium sulfate, talc powder, and hydrotalcite; preferably ,
  • the thermal curing accelerator is a latent thermal curing accelerator, more preferably the thermal curing accelerator is selected from the group consisting of boron trifluoride ethylamine complex, adipic acid dihydrazide, p-hydroxybenzoic acid hydrazide, isophthalic acid hydrazide One or more of hydrazine, diaminodiphenyl sulfone, dicyandiamide and its derivatives.
  • the resin composition includes 100 parts of alkali-soluble resin, 5-30 parts of acrylate monomer, 0.1-10 parts of photoinitiator, 10-30 parts of first epoxy resin, 0-15 parts of second epoxy resin, 5-7 parts of toughening resin, 1-5 parts of pigments and fillers, and 1-5 parts of additives.
  • the application of the above-mentioned resin composition in the field of high-frequency and high-speed printed circuit boards is also provided.
  • a method for preparing a high-frequency and high-speed printed circuit board solder resist protective layer which includes the following steps: roll coating the above-mentioned resin composition into a film to form a wet film; After pre-drying, hot roll filming, exposure, development, and thermal curing are performed in sequence to obtain a solder resist protective layer.
  • the wet film has a thickness of 25-50 ⁇ m; preferably, during the pre-drying process, the pre-drying temperature is 80°C-100°C and the time is 15-30 minutes;
  • the exposure energy during the process is 100 ⁇ 500mJ cm -2 ; preferably, the developing solution used in the development process is 0.8 ⁇ 1.2wt% Na 2 CO 3 solution, the development time is 30 ⁇ 60s, and the development temperature is 27 ⁇ 33°C ,
  • the spray pressure is 0.2 to 0.4 MPa; preferably, during the thermal curing process, the thermal curing temperature is 150 to 200° C., and the thermal curing time is 1 to 1.5 h.
  • the resin composition provided by the present invention includes 100 parts by weight of alkali-soluble resin, 5-30 parts of acrylic monomer, 0.1-10 parts of photoinitiator, 10-30 parts of first epoxy resin and 0-15 parts of the second epoxy resin; wherein the first epoxy resin is a low-dielectric epoxy resin with a dielectric constant of less than 3.5, and the second epoxy resin is different from the first epoxy resin.
  • the resin composition significantly reduces its dielectric constant and dielectric loss, and the dielectric constant can be reduced to below 3.0 , The dielectric loss can be reduced to less than 0.008.
  • the resin composition In addition to good dielectric properties, the resin composition also has good heat resistance, resolution, low rebound force, and relatively good flexibility and bending resistance. At the same time, the resin composition is a photosensitive resin composition and can perform image transfer by photosensitive development. The above reasons enable the resin composition of the present invention to meet the requirements of high-frequency and high-speed PCB and FPC circuit boards, and has broad application prospects.
  • the resin composition for printed circuit boards in the prior art is not suitable for application in high-frequency and high-speed printed circuit boards due to excessively high dielectric constant or dielectric loss.
  • the present invention provides a resin composition, which is characterized in that, by weight, the resin composition includes 100 parts of alkali-soluble resin, 5-30 parts of acrylic monomer, 0.1-10 parts by weight. Parts of photoinitiator, 10-30 parts of the first epoxy resin and 0-15 parts of the second epoxy resin; wherein the first epoxy resin is a low-dielectric epoxy resin with a dielectric constant ⁇ 3.5, and the second The epoxy resin is different from the first epoxy resin.
  • the above-mentioned resin composition provided by the present invention significantly reduces its dielectric constant and dielectric loss by adding a low dielectric epoxy resin with a dielectric constant of ⁇ 3.5, and then adjusting the proportion of each component, and the dielectric constant can be When it falls below 3.0, the dielectric loss can be reduced to below 0.008.
  • the resin composition also has good heat resistance, resolution, low rebound force, and relatively good flexibility and bending resistance.
  • the resin composition is a photosensitive resin composition and can perform image transfer by photosensitive development. The above reasons enable the resin composition of the present invention to meet the requirements of high-frequency and high-speed PCB and FPC circuit boards, and has broad application prospects.
  • the low-dielectric epoxy resin contains at least two epoxy groups, and the epoxy equivalent is 160 ⁇ 2000g/eq epoxy resin.
  • the low dielectric epoxy resin includes, but is not limited to, biphenyl type epoxy resin, naphthalene ring type epoxy resin, naphthol type epoxy resin, naphthylene ether type epoxy resin, and polyphenylene ether type epoxy resin. , One or more of dicyclopentadiene-type novolac epoxy resin and crystalline epoxy resin, more preferably naphthalene ring-type epoxy resin.
  • low dielectric epoxy resins can not only reduce the dielectric constant and dielectric loss of the resin composition, but also help improve the heat resistance and other properties of the resin composition. They are all fluorine-free epoxy resins. Resin also has a great advantage in terms of preparation cost.
  • the above several types of low dielectric epoxy resins respectively have the following chemical structures:
  • Biphenyl type epoxy resin has the structure shown in formula I:
  • n is a natural number from 1 to 10;
  • the naphthalene ring epoxy resin has the structure shown in formula II:
  • n is a natural number from 1 to 10;
  • the naphthol type epoxy resin has the structure shown in formula III:
  • n is a natural number from 1 to 10;
  • the naphthylene ether type epoxy resin has the structure shown in formula IV:
  • Polyphenylene ether type epoxy resin has the structure shown in formula V:
  • x and y are natural numbers from 1 to 10 respectively
  • Dicyclopentadiene type novolac epoxy resin has the structure shown in formula VI:
  • n is a natural number from 1 to 10;
  • the crystalline fluorene epoxy resin has the structure shown in formula VII:
  • the low-dielectric epoxy resins of these several structures are applied to the resin composition, which can further improve the various properties of the resin composition, making it more suitable for high-frequency and high-speed printed circuit boards as its solder resist protective layer material. It should be noted that the above-mentioned low-dielectric epoxy resins are commercially available.
  • the above-mentioned second epoxy resin may be other general-purpose epoxy resins except low-dielectric epoxy resin.
  • the above-mentioned second epoxy resin includes but is not limited to Nanya epoxy resin NPES-901, NPEL-128, NPES-904, NPCN704, or DIC epoxy resin Epiclon-1050, Epiclon-830, Epiclon N -One or more of 695.
  • the acid value of the above-mentioned alkali-soluble resin is 60-150 mg KOH/g.
  • the alkali-soluble resin is selected from one or more of photosensitive epoxy acrylic resin, styrene acrylic resin, and photosensitive urethane acrylic resin.
  • the photosensitive epoxy acrylic resin includes, but is not limited to, carboxylic acid modified bisphenol A type epoxy resin, carboxylic acid modified bisphenol F type epoxy resin, carboxylic acid modified novolac epoxy resin, carboxylic acid One or more of modified o-cresol epoxy resins.
  • the photosensitive epoxy acrylic resin the following commercially available products can also be used: Nippon Kayaku's ZAR-1035, ZAR-2000, ZAR-1000, ZFR-1491H, CCR-1291H, CCR-1235, etc.
  • the styrene acrylic resin is selected from carboxylic acid-modified benzene acrylic resins with a weight average molecular weight of 3-20w and a glass transition temperature of 90-150°C; preferably, the photosensitive polyurethane acrylic resin includes but is not limited to aliphatic polyurethane acrylic resin , One or more of alicyclic urethane acrylic resin and aromatic urethane acrylic resin. After using the above alkali-soluble resin, the overall performance of the resin composition is better.
  • the above-mentioned acrylate monomers can be of types commonly used in the field of photocuring, for example, monofunctional or multifunctional acrylate monomers can be used.
  • the weight-average molecular weight of the above-mentioned acrylate monomer is 200-2000, and the glass transition temperature is -20-100°C, so that the hardness, flexibility, resilience and resilience of the cured film can be controlled. Developability.
  • acrylic monomers include but are not limited to (ethoxy) phenol (meth) acrylate, stearate acrylate, ethoxy (propoxy) nonyl phenol (meth) acrylate, ethyl Oxy (propoxy) tetrahydrofurfuryl (meth)acrylate, 1,6-hexanediol diacrylate, PPG (400) diacrylate, tricyclodecane dimethanol diacrylate, dioxa Cyclohexanediol diacrylate, ethoxylated (propoxylated) bisphenol A di(meth)acrylate, polyethylene glycol (400) diacrylate, polypropylene glycol (600) diacrylate, ethoxy ( Propoxy) trimethylolpropane tri(meth)acrylate, pentaerythritol triacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, dipentaerythritol hexaacryl
  • the photoinitiator includes a photopolymerization initiator and a photosensitizer, and the weight ratio of the photopolymerization initiator to the photosensitizer is 2-20:1 .
  • the use of the photosensitizer helps to improve the photosensitive performance of the resin composition, and the ratio of the two is controlled within the above range, and the photocurable performance of the resin composition is better.
  • the photopolymerization initiator includes, but is not limited to, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-[4-(2-hydroxy)- Phenyl)-3-hydroxy-2-methyl-1-acetone-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-acetone, 2-benzene Benzyl-2-dimethylamine-1-(4-morpholinebenzylphenyl)butanone, 2,4,6-trimethylbenzoyl-diphenylphosphorus oxide, bis(2,4,6 -Trimethylbenzoyl) phenyl phosphine oxide, 2,4,6-trimethyl benzoyl phenyl phosphonate ethyl ester; preferably, the photosensitizer includes but not limited to 2, Diethyl 4-oxalate, 2-isopropylthioxanthone, 2,4-diethylthioxan
  • the resin composition further includes 3-10 parts by weight of toughening resin.
  • the use of toughening resin is beneficial to improve the flexural properties of the protective layer formed by the resin composition, and the protective layer has better performance in terms of heat resistance and resilience.
  • the toughening resin includes, but is not limited to, one or more of core-shell rubber toughened epoxy resin, thermoplastic elastomer, polyurethane elastomer, and rubber powder.
  • the core-shell rubber toughened epoxy resin commercially available can use Kaneka's MX154, MX113, MX158, M257, etc.
  • Thermoplastic elastomers can use styrene-butadiene block copolymer (SBS), styrene-poly(ethylene-ethylene/propylene) block-polystyrene (SEEPS), styrene-isoprene-styrene Block copolymer (SIS), etc.; commercially available polyurethane elastomers can use Dainichiseika’s RHC-730, Negami Chemical Industry’s Artpearl C-300T, Artpearl C-400T, Artpearl C-600T, Artpearl SE-050T, Artpearl GR- 50W, etc.; rubber powder commercially available products can use Kaneka's MZ100, MZ 210, MZ711, etc.
  • SBS styrene-butadiene block copolymer
  • SEEPS styrene-poly(ethylene-ethylene/propylene) block-polystyrene
  • the resin composition further includes 0-5 parts of pigments and fillers and 0.01-1 parts of auxiliary agents.
  • the above-mentioned pigments, fillers and auxiliary agents can be of common types in this field.
  • the pigment is selected from benzidine yellow, phthalocyanine green, phthalocyanine blue, carbon black and the like.
  • fillers such as silica, barium sulfate, calcium sulfate, talc, hydrotalcite, and the like at the same time.
  • the auxiliary agent is selected from one or more of thermal curing accelerators, dispersants, leveling agents, and defoamers.
  • the selection of a thermal curing accelerator helps to improve the thermal curing performance of the resin composition, and from the perspective of extending the storage period and improving the storage performance at room temperature, the thermal curing accelerator is more preferably a latent thermal curing accelerator, and a thermal curing accelerator is more preferable
  • boron trifluoride ethylamine complex adipic acid dihydrazide, p-hydroxybenzoic acid hydrazide, isophthalic acid hydrazide, diaminodiphenyl sulfone, dicyandiamide and its derivativeskind or more.
  • dispersants helps to improve the stability, wettability, dispersibility, and film forming properties of the resin composition, such as BYK9077, BYK110, BYK168 and other wetting and dispersing agents, BYK394, BYK322, BYK UV3530 and other leveling agents; BYK015, BYK1730, BYK354 and other defoamers.
  • the resin composition includes 100 parts of alkali-soluble resin, 5-30 parts of acrylate monomer, 0.1-10 parts of photoinitiator, and 10-30 parts of The first epoxy resin, 0-15 parts of the second epoxy resin, 3-10 parts of toughening resin, 1-5 parts of pigments and fillers, and 1-5 parts of additives. If the weight relationship of each component is controlled within the above range, the performance of the resin composition is better, and it is more suitable as a solder resist protective layer material for high-frequency and high-speed printed circuit boards.
  • the application of the above-mentioned resin composition in the field of high-frequency and high-speed printed circuit boards is also provided.
  • a method for preparing a solder resist protective layer for a high-frequency and high-speed printed circuit board which includes the following steps: roll coating the above-mentioned resin composition into a film to form a wet film; After pre-drying, hot roll filming, exposure, development, and thermal curing are performed in sequence to obtain a solder resist protective layer.
  • the formed high-frequency and high-speed printed circuit board (PCB, FPC, etc.) has lower dielectric constant and dielectric loss, and has good performance in terms of heat resistance, bendability, resilience, and resolution.
  • the thickness of the wet film is 25-50 ⁇ m; preferably, during the pre-drying process, the pre-drying temperature is 80-100°C and the time is 15-30min; preferably, the temperature during the exposure process
  • the exposure energy is 100 ⁇ 500mJ cm -2 ; preferably, the developing solution used in the development process is 0.8 ⁇ 1.2wt% Na 2 CO 3 solution, the development time is 30 ⁇ 60s, the development temperature is 27 ⁇ 33°C, spray
  • the pressure is 0.2 to 0.4 MPa; preferably, during the thermal curing process, the thermal curing temperature is 150 to 200° C., and the thermal curing time is 1 to 1.5 h.
  • a resin composition for high-frequency and high-speed printed circuit boards 15g alkali-soluble acrylic resin (acid value 120mgKOH/g, molecular weight 150,000), 2.5g acrylate monomer (including 1.5g 20EOBPDMA, 1.0g 10EOTMPTA) , 0.1g photopolymerization initiator (including 0.04g 184, 0.06g 907), 0.01g photosensitizer (ITX), 3.5g epoxy resin (including 1.8g naphthalene ring type low dielectric epoxy resin, 0.9g NPES-901 , 0.8g toughened epoxy resin MX-154), 0.01g boron trifluoride ethylamine latent curing accelerator, 0.3g carbon black MA-7, 0.5g other additives (including 0.3g dispersant BYK168, 0.1g Leveling agent BYK 394, 0.1g defoaming agent BYK354), firstly grind with three rollers, then dissolve and disperse with high-speed stirring,
  • 20EOBPDMA is 20 ethoxy bisphenol A dimethacrylate (Sartomer Co., Ltd.)
  • 10EOTMPTA is 10 ethoxy trimethylolpropane triacrylate (Sartomer Co., Ltd.)
  • NPES-901 solid epoxy resin, manufactured in Nanya, epoxy equivalent 450-500g/eq
  • MX-154 core-shell rubber toughened epoxy resin, Kaneka, epoxy equivalent 301g/eq, polybutadiene rubber
  • Carbon black MA-7 Mitsubishi Chemical, average particle size 24nm, pH value 3.0, furnace black
  • the cured films in the examples and the comparative examples were subjected to a 180° angle folding test, and the number of times that cracks started to appear was recorded and evaluated based on the following criteria.
  • the cured film was immersed vertically in a tin furnace at a temperature of 300°C for 3 times for 10 seconds each time. Observe whether the surface is blistered, discolored, floated, peeled, etc., and evaluate the appearance change based on the following criteria.
  • the cured film has floating, thin separation and deep soldering
  • the cured films obtained in the examples and comparative examples were dried at 150°C for 30 minutes, and measured at 10GHz for each resin composition using a resonator (Agilent E5071BENA) under the conditions of 25°C and 50% RH by the separation dielectric resonator (SPDR) method Dielectric constant and dielectric loss at frequency.
  • a resonator Alent E5071BENA
  • SPDR separation dielectric resonator
  • the cured film was placed in a constant temperature and humidity box at 85°C and 85% RH for 24 hours, and then the surface resistance and volume resistance of the cured film were tested.
  • the test conditions were 50V, 1min.
  • adding a low-dielectric epoxy resin to the photosensitive resin composition can improve the dielectric properties of the cured film, and significantly reduce the dielectric constant and dielectric loss factor.
  • the dielectric constant is reduced from 3.5 to below 3.0.
  • the electrical loss factor is reduced from 0.012 to less than 0.008, which meets the requirements of high-frequency and high-speed PCBs and FPCBs, thereby obtaining a photosensitive solder resist protective layer with both high resolution and excellent dielectric properties.
  • the special molecular structure of the low-dielectric epoxy resin can further improve the heat resistance of the cured film and has less impact on its rebound force, so as not to reduce the flexibility and bending resistance of the solder mask protective layer.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

一种树脂组合物及其应用，该树脂组合物按重量份计包括100份的碱溶性树脂、5～30份的丙烯酸酯类单体、0.1～10份的光引发剂、10～30份的第一环氧树脂和0～15份的第二环氧树脂；第一环氧树脂为介电常数＜3.5的低介电环氧树脂，第二环氧树脂不同于第一环氧树脂。该树脂组合物通过添加介电常数＜3.5的低介电环氧树脂，再通过调整各组分的配比，显著降低了介电常数和介电损耗，介电常数降至3.0以下，介电损耗降至0.008以下。此外，该树脂组合物还兼具了良好的耐热性、解像度，反弹力较小，且具有相对较好的柔韧性和耐弯折性。同时，该树脂组合物为感光性树脂组合物，能够通过感光显影进行图像转移。

Description

树脂组合物及其应用 技术领域
本发明涉及线路板印刷技术领域，具体而言，涉及一种树脂组合物及其应用，尤其涉及一种高频高速印刷线路板用的树脂组合物。
背景技术
随着5G时代的到来，当前小型化、薄型化、高集成化、全面屏的形态趋势，使得终端设备对支撑材料的要求越来越高。由于5G信号在传输过程中将采用更高的频率、更快的传输速度，要求PCB及FPCB材料能降低在高频区域、具体而言为频率1GHz以上的区域中的电信号损耗，这就要求PCB及FPCB材料具有较低的介电常数(Dk)和介电损耗(Df)。其中，Dk要小于等于3.0，Df要小于等于0.008。
在现有技术中，感光性聚酰亚胺覆盖膜具有较低的Dk，为3.0以下，但Df偏高超过0.01。传统PI覆盖膜(CVL)由环氧胶层和聚酰亚胺树脂层构成，而环氧胶层的极性较高导致传统CVL的Dk高达3.5以上。现有的阻焊油墨、弯曲性油墨以及PIC感光覆盖膜中均含有大量的高极性环氧树脂和较高浓度的极性基团，材料的介电性能也欠佳。
因此，业界迫切希望能有低介电常数和低介电损耗的感光性阻焊保护层材料(比如覆盖膜、阻焊油墨或者感光性覆盖膜等)。在覆铜板领域，低介电型材料的开发基本上多采用聚四氟乙烯树脂、马来酰亚胺树脂、热固性聚苯醚树脂、氰酸树脂、聚酰亚胺树脂、低介电环氧树脂以及液晶高分子聚合物；而在阻焊保护层领域，低介电覆盖膜、低介电阻焊油墨和低介电感光覆盖膜的研究较少。
中国专利CN108287451A公开了一种低介电感光覆盖膜树脂组合物，通过在环氧丙烯酸树脂体系中加入氟化聚合物来降低材料的介电常数，该氟化聚合粒径0.1-7微米，容易团聚析出且与主体树脂的相容性较差，影响材料整体的介电性和透光性。中国专利CN109923176A公开了用于高频信号传输性的低介电覆盖膜，其技术路线是通过加入低介电损耗的聚苯醚树脂以及咪唑化合物、低极性的联苯型、萘环骨架环氧树脂等来降低传统CVL中环氧胶层的介电常数，但该组合物跟传统CVL一样，无法通过感光显影来进行图像转移，依然需要模具冲切来开窗，开窗精度低，难以满足高精细、超薄集成线路板对解像度的要求。
基于以上原因，有必要提供在感光性、介电性、柔软性和加工性等方面表现更加的低介电感光性阻焊保护层材料。
发明内容
本发明的主要目的在于提供一种树脂组合物及其应用，以解决现有技术中的树脂组合物因感光性、介电性、柔软性或加工性方面的欠缺而不适于在高频高速印刷线路板中应用的问题。
为了实现上述目的，根据本发明的一个方面，提供了一种树脂组合物，按重量份计，该树脂组合物包括100份的碱溶性树脂、5～30份的丙烯酸酯类单体、0.1～10份的光引发剂、10～30份的第一环氧树脂和0～15份的第二环氧树脂；其中第一环氧树脂为介电常数＜3.5的低介电环氧树脂，第二环氧树脂不同于第一环氧树脂。
进一步地，低介电环氧树脂为至少含有两个环氧基、环氧当量为160～2000g/eq的环氧树脂；优选地，低介电环氧树脂为联苯型环氧树脂、萘环型环氧树脂、萘酚型环氧树脂、亚萘基醚型环氧树脂、聚苯醚型环氧树脂、双环戊二烯型酚醛环氧树脂、结晶性芴型环氧树脂中的一种或多种，更优选为萘环型环氧树脂。
进一步地，联苯型环氧树脂具有式I所示结构：
Figure PCTCN2020100911-appb-000001
n为1～10的自然数；
萘环型环氧树脂具有式II所示结构：
Figure PCTCN2020100911-appb-000002
n为1～10的自然数；
萘酚型环氧树脂具有式III所示结构：
Figure PCTCN2020100911-appb-000003
n为1～10的自然数；
亚萘基醚型环氧树脂具有式Ⅳ所示结构：
Figure PCTCN2020100911-appb-000004
n为1～10的自然数；
聚苯醚型环氧树脂具有式Ⅴ所示结构：
Figure PCTCN2020100911-appb-000005
x和y分别为1～10的自然数；
双环戊二烯型酚醛环氧树脂具有式Ⅵ所示结构：
Figure PCTCN2020100911-appb-000006
n为1～10的自然数；
结晶性芴型环氧树脂具有式Ⅶ所示结构：
Figure PCTCN2020100911-appb-000007
进一步地，碱溶性树脂的酸值为60～150mg KOH/g；优选地，碱溶性树脂选自感光性环氧丙烯酸树脂、苯丙烯树脂、感光性聚氨酯丙烯酸树脂中的一种或多种；优选地，感光性环氧丙烯酸树脂选自羧酸改性双酚A型环氧树脂、羧酸改性双酚F型环氧树脂、羧酸改性酚醛环氧树脂、羧酸改性邻甲酚醛环氧树脂中的一种或多种；优选地，苯丙烯树脂选自重均分子量为3～20w、玻璃化转变温度为90～150℃的羧酸改性苯丙烯酸树脂；优选地，感光性聚氨酯丙烯酸树脂选自脂肪族聚氨酯丙烯酸树脂、脂环族聚氨酯丙烯酸树脂、芳香族聚氨酯丙烯酸树脂中的一种或多种。
进一步地，丙烯酸酯类单体的重均分子量为200～2000，玻璃化转变温度为-20～100℃；优选地，丙烯酸酯类单体选自(乙氧基)苯酚(甲基)丙烯酸酯、硬脂酸丙烯酸酯、乙氧基(丙氧基)壬基苯酚(甲基)丙烯酸酯、乙氧基(丙氧基)四氢糠基(甲基)丙烯酸酯、1,6-己二醇二丙烯酸酯、PPG(400)二丙烯酸酯、三环葵烷二甲醇二丙烯酸酯、二氧杂环己烷二醇二丙烯酸酯、乙氧化(丙氧化)双酚A二(甲基)丙烯酸酯、聚乙二醇(400)二丙烯酸酯、聚丙二醇(600)二丙烯酸酯、乙氧基(丙氧基)三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇三丙烯酸酯、三(2-羟乙基)异氰尿酸三丙烯酸酯、六丙烯酸二季戊四醇酯、乙氧基化季戊四醇四丙烯酸酯、双季戊四醇六丙烯酸酯中的一种或多种。
进一步地，光引发剂包括光聚合引发剂和光敏剂，且光聚合引发剂和光敏剂的重量比为2～20:1；优选地，光聚合引发剂选自1-羟基环己基苯基甲酮、2-羟基-2-甲基-1-苯基-1-丙酮、1-[4-(2-羟基)-苯基]-3-羟基-2-甲基-1-丙酮-1-酮、2-甲基-1-(4-甲硫基苯基)-2-吗啉-1-丙酮、2-苯基苄-2-二甲基胺-1-(4-吗啉苄苯基)丁酮、2,4,6-三甲基苯甲酰-二苯基氧化磷、双(2,4,6-三甲 基苯甲酰基)苯基氧化膦、2,4,6-三甲基苯甲酰基苯基膦酸乙酯中的一种或多种；优选地，光敏剂选自2,4-乙二酸二乙酯、2-异丙基硫杂蒽酮、2,4-二乙基硫杂蒽酮、二苯甲酮、聚丁二醇双(9-氧代-9H-噻吨氧乙酸)酯中的一种或多种。
进一步地，按重量份计，树脂组合物还包括3～10份的增韧树脂；优选地，增韧树脂选自核壳橡胶增韧环氧树脂、热塑性弹性体、聚氨酯弹性体、液体橡胶、橡胶粉中的一种或多种。
进一步地，按重量份计，树脂组合物还包括0～5份的颜填料和0.01～5份的添加剂，添加剂选自热固化促进剂、分散剂、流平剂、消泡剂中的一种或多种；优选地，颜填料选自联苯胺黄、酞菁绿、酞菁蓝、炭黑、二氧化硅、硫酸钡、硫酸钙、滑石粉、水滑石中的一种多种；优选地，热固化促进剂为潜伏型热固化促进剂，更优选热固化促进剂选自三氟化硼乙胺络合物、己二酸二酰肼、对羟基安息香酸酰肼、间苯二甲酸酰肼、二胺基二苯砜、双氰胺及其衍生物中的一种或多种。
进一步地，按重量份计，树脂组合物包括100份的碱溶性树脂、5～30份的丙烯酸酯类单体、0.1～10份的光引发剂、10～30份的第一环氧树脂、0～15份的第二环氧树脂、5～7份的增韧树脂、1～5份的颜填料和1～5份的添加剂。
根据本发明的另一方面，还提供了上述树脂组合物在高频高速印刷线路板领域的应用。
根据本发明的另一方面，还提供了一种高频高速印刷线路板阻焊保护层的制备方法，其包括以下步骤：将上述树脂组合物进行辊涂成膜，形成湿膜；将湿膜进行预烘干后，依次进行热辊贴膜、曝光、显影、热固化，得到阻焊保护层。
根据本发明的另一方面，还提供了湿膜的厚度为25～50μm；优选地，预烘干过程中，预烘干温度为80℃～100℃，时间为15～30min；优选地，曝光过程中的曝光能量为100～500mJ cm -2；优选地，显影过程中，采用的显影液为0.8～1.2wt％Na 2CO 3溶液，显影时间为30～60s，显影温度为27～33℃，喷淋压力为0.2～0.4MPa；优选地，热固化过程中，热固化温度为150～200℃，热固化时间为1～1.5h。
本发明提供的树脂组合物按重量份计包括100份的碱溶性树脂、5～30份的丙烯酸酯类单体、0.1～10份的光引发剂、10～30份的第一环氧树脂和0～15份的第二环氧树脂；其中第一环氧树脂为介电常数＜3.5的低介电环氧树脂，所述第二环氧树脂不同于所述第一环氧树脂。该树脂组合物通过添加介电常数＜3.5的低介电环氧树脂，再通过调整各组分的配比，显著地降低了其介电常数和介电损耗，介电常数能够降至3.0以下，介电损耗能够降至0.008以下。除了良好的介电性能，该树脂组合物还兼具了良好的耐热性、解像度，反弹力较小，且具有相对较好的柔韧性和耐弯折性。同时，该树脂组合物为感光性树脂组合物，能够通过感光显影进行图像转移。以上原因使得本发明的树脂组合物能够满足高频高速PCB和FPC线路板的要求，具有广阔的应用前景。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。
正如本发明背景技术部分所描述的，现有技术中的印刷线路板用树脂组合物因介电常数或介电损耗过高，不适于在高频高速印刷线路板中应用。
为了解决这一问题，本发明提供了一种树脂组合物，其特征在于，按重量份计，树脂组合物包括100份的碱溶性树脂、5～30份的丙烯酸酯类单体、0.1～10份的光引发剂、10～30份的第一环氧树脂和0～15份的第二环氧树脂；其中第一环氧树脂为介电常数＜3.5的低介电环氧树脂，第二环氧树脂不同于第一环氧树脂。
本发明提供的上述树脂组合物通过添加介电常数＜3.5的低介电环氧树脂，再通过调整各组分的配比，显著地降低了其介电常数和介电损耗，介电常数能够降至3.0以下，介电损耗能够降至0.008以下。除了良好的介电性能，该树脂组合物还兼具了良好的耐热性、解像度，反弹力较小，且具有相对较好的柔韧性和耐弯折性。同时，该树脂组合物为感光性树脂组合物，能够通过感光显影进行图像转移。以上原因使得本发明的树脂组合物能够满足高频高速PCB和FPC线路板的要求，具有广阔的应用前景。
为了进一步提高树脂组合物的锡焊耐热性、显影性、粘附性等，在一种优选的实施方式中，上述低介电环氧树脂为至少含有两个环氧基、环氧当量为160～2000g/eq的环氧树脂。优选地，低介电环氧树脂包括但不限于联苯型环氧树脂、萘环型环氧树脂、萘酚型环氧树脂、亚萘基醚型环氧树脂、聚苯醚型环氧树脂、双环戊二烯型酚醛环氧树脂、结晶型环氧树脂中的一种或多种，更优选为萘环型环氧树脂。上述几类低介电环氧树脂除了能够降低树脂组合物的介电常数和介电损耗外，还有助于提高树脂组合物的耐热性等其他性能，且均为不含氟的环氧树脂，在制备成本方面也具有较大优势。
更优选地，上述几类低介电环氧树脂分别具有以下化学结构：
联苯型环氧树脂具有式I所示结构：
Figure PCTCN2020100911-appb-000008
n为1～10的自然数；
萘环型环氧树脂具有式II所示结构：
Figure PCTCN2020100911-appb-000009
n为1～10的自然数；
萘酚型环氧树脂具有式III所示结构：
Figure PCTCN2020100911-appb-000010
n为1～10的自然数；
亚萘基醚型环氧树脂具有式Ⅳ所示结构：
Figure PCTCN2020100911-appb-000011
聚苯醚型环氧树脂具有式Ⅴ所示结构：
Figure PCTCN2020100911-appb-000012
x和y分别为1～10的自然数
双环戊二烯型酚醛环氧树脂具有式Ⅵ所示结构：
Figure PCTCN2020100911-appb-000013
n为1～10的自然数；
结晶性芴型环氧树脂具有式Ⅶ所示结构：
Figure PCTCN2020100911-appb-000014
这几种结构的低介电环氧树脂应用于树脂组合物，能够进一步改善树脂组合物的各项性能，使其更适用于高频高速印刷电路板中，作为其阻焊保护层材料。需说明的是，上述几种低介电环氧树脂均可商购。
上述第二环氧树脂可以采用除低介电环氧树脂以外的其他通用型环氧树脂，当然，考虑到与低介电环氧树脂的相容性及对树脂组合物性能的提升，在一种优选的实施方式中，上述第二环氧树脂包括但不限于南亚环氧树脂NPES-901、NPEL-128、NPES-904、NPCN704、或DIC环氧树脂Epiclon-1050、Epiclon-830、Epiclon N-695中的一种或多种。
在一种优选的实施方式中，上述碱溶性树脂的酸值为60～150mg KOH/g，当酸值低于60mg KOH/g时，显影较差，产生残胶等显影不尽的问题；而当酸值高于150mg KOH/g时，显影过度导致线宽、线距偏离标准值。优选地，碱溶性树脂选自感光性环氧丙烯酸树脂、苯丙烯树脂、感光性聚氨酯丙烯酸树脂中的一种或多种。这几类碱溶性树脂的使用能够进一步提高树脂组合物的感光显影能力，从而有利于提高树脂组合物成膜后的解像度，满足线路板的高精度要求。其中，优选地，感光性环氧丙烯酸树脂包括但不限于羧酸改性双酚A型环氧树脂、羧酸改性双酚F型环氧树脂、羧酸改性酚醛环氧树脂、羧酸改性邻甲酚醛环氧树脂中的一种或多种。感光性环氧丙烯酸树脂也可采用以下市售品：日本化药的ZAR-1035、ZAR-2000、ZAR-1000、ZFR-1491H、CCR-1291H、CCR-1235等。优选地，苯丙烯树脂选自重均分子量为3～20w、玻璃化转变温度为90～150℃的羧酸改性苯丙烯酸树脂；优选地，感光性聚氨酯丙烯酸树脂包括但不限于脂肪族聚氨酯丙烯酸树脂、脂环族聚氨酯丙烯酸树脂、芳香族聚氨酯丙烯酸树脂中的一种或多种。使用以上碱溶性树脂后，树脂组合物综合性能更佳。
上述丙烯酸酯类单体可以采用光固化领域常用的类型，比如可以使用单官能或多官能丙烯酸酯类单体。在一种优选的实施方式中，上述丙烯酸酯类单体的重均分子量为200～2000，玻璃化转变温度为-20～100℃，由此可调控固化膜的硬度、柔韧性、反弹力和显影性。优选地，丙烯酸酯类单体包括但不限于(乙氧基)苯酚(甲基)丙烯酸酯、硬脂酸丙烯酸酯、乙氧基(丙氧基)壬基苯酚(甲基)丙烯酸酯、乙氧基(丙氧基)四氢糠基(甲基)丙烯酸酯、1,6-己二醇二丙烯酸酯、PPG(400)二丙烯酸酯、三环葵烷二甲醇二丙烯酸酯、二氧杂环己烷二醇二丙烯酸酯、乙氧化(丙氧化)双酚A二(甲基)丙烯酸酯、聚乙二醇(400)二丙烯酸酯、聚丙二醇(600)二丙烯酸酯、乙氧基(丙氧基)三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇三丙烯酸酯、三(2-羟乙基)异氰尿酸三丙烯酸酯、六丙烯酸二季戊四醇酯、乙氧基化季戊四醇四丙烯酸酯、双季戊四醇六丙烯酸酯中的一种或多种。
为了进一步改善树脂组合物的光固化性能，在一种优选的实施方式中，上述光引发剂包括光聚合引发剂和光敏剂，且光聚合引发剂和光敏剂的重量比为2～20:1。光敏剂的使用有助于提高树脂组合物的感光性能，且将二者比例控制在上述范围内，树脂组合物的光固化性能更佳。优选地，光聚合引发剂包括但不限于1-羟基环己基苯基甲酮、2-羟基-2-甲基-1-苯基-1-丙酮、1-[4-(2-羟基)-苯基]-3-羟基-2-甲基-1-丙酮-1-酮、2-甲基-1-(4-甲硫基苯基)-2-吗啉-1-丙酮、2-苯基苄-2-二甲基胺-1-(4-吗啉苄苯基)丁酮、2,4,6-三甲基苯甲酰-二苯基氧化磷、双(2,4,6-三甲基苯甲酰基)苯基氧化膦、2,4,6-三甲基苯甲酰基苯基膦酸乙酯中的一种或多种；优选地，光敏剂包括但不限于2,4-乙二酸二乙酯、2-异丙基硫杂蒽酮、2,4-二乙基硫杂蒽酮、二苯甲酮、聚丁二醇双(9-氧代-9H-噻吨氧乙酸)酯中的一种或多种。
在一种优选的实施方式中，按重量份计，树脂组合物还包括3～10份的增韧树脂。使用增韧树脂有利于提高树脂组合物形成的保护层的弯折性，并是保护层在耐热性、反弹力等方面的表现更佳。优选地，增韧树脂包括但不限于核壳橡胶增韧环氧树脂、热塑性弹性体、聚氨酯弹性体、橡胶粉中的一种或多种。核壳橡胶增韧环氧树脂市售品可采用Kaneka的MX154、MX113、MX158、M257等。热塑性弹性体可采用苯乙烯-丁二烯嵌段共聚物(SBS)、苯乙烯- 聚(乙烯-乙烯/丙烯)嵌段-聚苯乙烯(SEEPS)、苯乙烯-异戊二烯-苯乙烯嵌段共聚物(SIS)等；聚氨酯弹性体市售品可采用Dainichiseika的RHC-730，Negami Chemical Industry的Artpearl C-300T、Artpearl C-400T、Artpearl C-600T、Artpearl SE-050T、Artpearl GR-50W等；橡胶粉市售品可采用Kaneka的MZ100、MZ 210、MZ711等。
为了进一步提高树脂组合物的综合性能，在一种优选的实施方式中，按重量份计，树脂组合物还包括0～5份的颜填料和0.01～1份的助剂。上述颜填料和助剂可以采用本领域的常用类型，优选地，颜料选自联苯胺黄、酞菁绿、酞菁蓝、炭黑等。为了提高耐热性、降低成本，优选同时加入填料，比如二氧化硅、硫酸钡、硫酸钙、滑石粉、水滑石等。优选地，助剂选自热固化促进剂、分散剂、流平剂、消泡剂中的一种或多种。选用热固化促进剂有助于提高树脂组合物的热固化性能，且从延长储存期、提高常温保存性角度出发，更优选热固化促进剂为潜伏型热固化促进剂，进一步优选热固化促进剂选自三氟化硼乙胺络合物、己二酸二酰肼、对羟基安息香酸酰肼、间苯二甲酸酰肼、二胺基二苯砜、双氰胺及其衍生物中的一种或多种。使用分散剂、流平剂和消泡剂有助于提高树脂组合物的稳定性、润湿性、分散性、成膜性等，比如BYK9077、BYK110、BYK168等润湿分散剂，BYK394、BYK322、BYK UV3530等流平剂；BYK015、BYK1730、BYK354等消泡剂。
在一种优选的实施方式中，按重量份计，树脂组合物包括100份的碱溶性树脂、5～30份的丙烯酸酯类单体、0.1～10份的光引发剂、10～30份的第一环氧树脂、0～15份的第二环氧树脂、3～10份的增韧树脂、1～5份的颜填料和1～5份的添加剂。将各组分的重量关系控制在上述范围内，树脂组合物的性能更佳，更适于作为高频高速印刷线路板的阻焊保护层材料。
根据本发明的另一方面，还提供了上述树脂组合物在高频高速印刷线路板领域的应用。
根据本发明的有一方面，还提供了一种高频高速印刷线路板阻焊保护层的制备方法，其包括以下步骤：将上述树脂组合物进行辊涂成膜，形成湿膜；将湿膜进行预烘干后，依次进行热辊贴膜、曝光、显影、热固化，得到阻焊保护层。采用上述树脂组合物，形成的高频高速印刷线路板(PCB、FPC等)的介电常数和介电损耗更低，且在耐热性、弯折性、反弹力、解像度等方面表现良好。
在一种优选的实施方式中，湿膜的厚度为25～50μm；优选地，预烘干过程中，预烘干温度为80～100℃，时间为15～30min；优选地，曝光过程中的曝光能量为100～500mJ cm -2；优选地，显影过程中，采用的显影液为0.8～1.2wt％Na 2CO 3溶液，显影时间为30～60s，显影温度为27～33℃，喷淋压力为0.2～0.4MPa；优选地，热固化过程中，热固化温度为150～200℃，热固化时间为1～1.5h。
以下结合具体实施例对本申请作进一步详细描述，这些实施例不能理解为限制本申请所要求保护的范围。
实施例1
一种用于高频高速印刷线路板的树脂组合物的制备：15g碱溶性光敏环氧丙烯酸树脂ZAR-1035(酸值100mgKOH/g，固含量64％)，2.5g丙烯酸酯单体(其中1.5g 20EOBPDMA、1.0g 10EOTMPTA)，0.5g光聚合引发剂(其中0.2g 184、0.3g 907)、0.05g光敏剂(ITX)，3.5g环氧树脂(其中2.7g萘环型低介电环氧树脂、0.8g增韧环氧树脂MX-154)，0.01g三氟化硼乙胺潜伏型固化促进剂，0.3g炭黑MA-7，0.5g其他助剂(其中0.3g分散剂BYK168、0.1g流平剂BYK 394、0.1g消泡剂BYK354)，先经三辊研磨、然后高速搅拌溶解、分散，最后过滤制得胶液，暗光保存备用。
实施例2
一种用于高频高速印刷线路板的树脂组合物的制备：15g碱溶性光敏环氧丙烯酸树脂ZAR-1035(酸值100mgKOH/g，固含量64％)，2.5g丙烯酸酯单体(其中1.5g 20EOBPDMA、1.0g 10EOTMPTA)，0.5g光聚合引发剂(其中0.2g 184、0.3g 907)、0.05g光敏剂(ITX)，3.5g环氧树脂(其中1.8g萘环型低介电环氧树脂、0.9g NPES-901、0.8g增韧环氧树脂MX-154)，0.01g三氟化硼乙胺潜伏型固化促进剂，0.3g炭黑MA-7，0.5g其他助剂(其中0.3g分散剂BYK168、0.1g流平剂BYK 394、0.1g消泡剂BYK354)，先经三辊研磨、然后高速搅拌溶解、分散，最后过滤制得胶液，暗光保存备用。
实施例3
一种用于高频高速印刷线路板的树脂组合物的制备：15g碱溶性光敏环氧丙烯酸树脂ZAR-1035(酸值100mgKOH/g，固含量64％)，2.5g丙烯酸酯单体(其中1.5g 20EOBPDMA、1.0g 10EOTMPTA)，0.5g光聚合引发剂(其中0.2g 184、0.3g 907)、0.05g光敏剂(ITX)，3.5g环氧树脂(其中0.96g萘环型低介电环氧树脂、1.44g NPES-901、0.8g增韧环氧树脂MX-154)，0.01g三氟化硼乙胺潜伏型固化促进剂，0.3g炭黑MA-7，0.5g其他助剂(其中0.3g分散剂BYK168、0.1g流平剂BYK 394、0.1g消泡剂BYK354)，先经三辊研磨、然后高速搅拌溶解、分散，最后过滤制得胶液，暗光保存备用。
实施例4
一种用于高频高速印刷线路板的树脂组合物的制备：15g碱溶性丙烯酸树脂(酸值120mgKOH/g，分子量15万)，2.5g丙烯酸酯单体(其中1.5g 20EOBPDMA、1.0g 10EOTMPTA)，0.1g光聚合引发剂(其中0.04g 184、0.06g 907)、0.01g光敏剂(ITX)，3.5g环氧树脂(其中1.8g萘环型低介电环氧树脂、0.9g NPES-901、0.8g增韧环氧树脂MX-154)，0.01g三氟化硼乙胺潜伏型固化促进剂，0.3g炭黑MA-7，0.5g其他助剂(其中0.3g分散剂BYK168、0.1g流平剂BYK 394、0.1g消泡剂BYK354)，先经三辊研磨、然后高速搅拌溶解、分散，最后过滤制得胶液，暗光保存备用。
实施例5
一种用于高频高速印刷线路板的树脂组合物的制备：15g碱溶性聚氨酯环氧丙烯酸树脂UXE3000(酸值100mgKOH/g，固含量64％)，2.5g丙烯酸酯单体(其中1.5g 20EOBPDMA、1.0g 10EOTMPTA)，0.5g光聚合引发剂(其中0.2g 184、0.3g 907)、0.05g光敏剂(ITX)，3.5g环氧树脂(其中1.8g萘环型低介电环氧树脂、0.9g NPES-901、0.8g增韧环氧树脂MX-154)，0.01g三氟化硼乙胺潜伏型固化促进剂，0.3g炭黑MA-7，0.5g其他助剂(其中0.3g分散剂BYK168、0.1g流平剂BYK 394、0.1g消泡剂BYK354)，先经三辊研磨、然后高速搅拌溶解、分散，最后过滤制得胶液，暗光保存备用。
实施例6
一种用于高频高速印刷线路板的树脂组合物的制备：15g碱溶性光敏环氧丙烯酸树脂ZAR-1035(酸值100mgKOH/g，固含量64％)，2.5g丙烯酸酯单体(其中1.5g 20EOBPDMA、1.0g 10EOTMPTA)，0.5g光聚合引发剂(其中0.2g 184、0.3g 907)、0.05g光敏剂(ITX)，10g环氧树脂(其中1.8g双环戊二烯型低介电环氧树脂、0.9g NPES-901、0.8g增韧环氧树脂MX-154)，0.01g三氟化硼乙胺潜伏型固化促进剂，0.3g炭黑MA-7，0.5g其他助剂(其中0.3g分散剂BYK168、0.1g流平剂BYK 394、0.1g消泡剂BYK354)，先经三辊研磨、然后高速搅拌溶解、分散，最后过滤制得胶液，暗光保存备用。
实施例7
一种用于高频高速印刷线路板的树脂组合物的制备：15g碱溶性光敏环氧丙烯酸树脂ZAR-1035(酸值100mgKOH/g，固含量64％)，2.5g丙烯酸酯单体(其中1.5g 20EOBPDMA、1.0g 10EOTMPTA)，0.5g光聚合引发剂(其中0.2g 184、0.3g 907)、0.05g光敏剂(ITX)，3.5g环氧树脂(其中2.1g双环戊二烯型低介电环氧树脂、1.4g NPES-901)，先经三辊研磨、然后高速搅拌溶解、分散，最后过滤制得胶液，暗光保存备用。
实施例8
一种用于高频高速印刷线路板的树脂组合物的制备：15g碱溶性光敏环氧丙烯酸树脂ZAR-1035(酸值100mgKOH/g，固含量64％)，2.5g丙烯酸酯单体(其中1.5g 20EOBPDMA、1.0g 10EOTMPTA)，0.5g光聚合引发剂(其中0.2g 184、0.3g 907)、0.05g光敏剂(ITX)，3.5g环氧树脂(其中1.8g联苯型低介电环氧树脂、0.9g NPES-901、0.8g增韧环氧树脂MX-154)，0.01g三氟化硼乙胺潜伏型固化促进剂，0.3g炭黑MA-7，0.5g其他助剂(其中0.3g分散剂BYK168、0.1g流平剂BYK 394、0.1g消泡剂BYK354)，先经三辊研磨、然后高速搅拌溶解、分散，最后过滤制得胶液，暗光保存备用。
实施例9
一种用于高频高速印刷线路板的树脂组合物的制备：15g碱溶性光敏环氧丙烯酸树脂ZAR-1035(酸值100mgKOH/g，固含量64％)，2.5g丙烯酸酯单体(其中1.5g 20EOBPDMA、 1.0g 10EOTMPTA)，0.5g光聚合引发剂(其中0.2g 184、0.3g 907)、0.05g光敏剂(ITX)，3.5g环氧树脂(其中1.8g结晶性芴型环氧树脂、0.9g NPES-901、0.8g增韧环氧树脂MX-154)，0.01g三氟化硼乙胺潜伏型固化促进剂，0.3g炭黑MA-7，0.5g其他助剂(其中0.3g分散剂BYK168、0.1g流平剂BYK 394、0.1g消泡剂BYK354)，先经三辊研磨、然后高速搅拌溶解、分散，最后过滤制得胶液，暗光保存备用。
实施例10
一种用于高频高速印刷线路板的树脂组合物的制备：15g碱溶性光敏环氧丙烯酸树脂ZAR-1035(酸值100mgKOH/g，固含量64％)，0.48g丙烯酸酯单体(其中0.29g 20EOBPDMA、0.19g 10EOTMPTA)，0.01g光聚合引发剂(其中0.004g 184、0.006g 907)、0.001g光敏剂(ITX)，3.5g环氧树脂(其中1.8g环戊二烯型低介电环氧树脂、0.9g NPES-901、0.8g增韧环氧树脂MX-154)，0.01g三氟化硼乙胺潜伏型固化促进剂，0.3g炭黑MA-7，0.5g其他助剂(其中0.3g分散剂BYK168、0.1g流平剂BYK 394、0.1g消泡剂BYK354)，先经三辊研磨、然后高速搅拌溶解、分散，最后过滤制得胶液，暗光保存备用。
实施例11
一种用于高频高速印刷线路板的树脂组合物的制备：15g碱溶性光敏环氧丙烯酸树脂ZAR-1035(酸值100mgKOH/g，固含量64％)，2.8g丙烯酸酯单体(其中1.7g 20EOBPDMA、1.1g 10EOTMPTA，0.96g光聚合引发剂(其中0.38g 184、0.58g 907)、0.1g光敏剂(ITX)，3.5g环氧树脂(其中1.8g双环戊二烯型低介电环氧树脂、0.9g NPES-901、0.8g增韧环氧树脂MX-154)，0.01g三氟化硼乙胺潜伏型固化促进剂，0.3g炭黑MA-7，0.5g其他助剂(其中0.3g分散剂BYK168、0.1g流平剂BYK 394、0.1g消泡剂BYK354)，先经三辊研磨、然后高速搅拌溶解、分散，最后过滤制得胶液，暗光保存备用。
对比例1
一种用于高频高速印刷线路板的树脂组合物的制备：15g碱溶性光敏环氧丙烯酸树脂ZAR-1035(酸值100mgKOH/g，固含量64％)，2.5g丙烯酸酯单体(其中1.5g 20EOBPDMA、1.0g 10EOTMPTA)，0.5g光聚合引发剂(其中0.2g 184、0.3g 907)、0.05g光敏剂(ITX)，3.5g环氧树脂(其中2.7g NPES-901、0.8g增韧环氧树脂MX-154)，0.01g三氟化硼乙胺潜伏型固化促进剂，0.3g炭黑MA-7，0.5g其他助剂(其中0.3g分散剂BYK168、0.1g流平剂BYK 394、0.1g消泡剂BYK354)，先经三辊研磨、然后高速搅拌溶解、分散，最后过滤制得胶液，暗光保存备用。
对比例2
一种用于高频高速印刷线路板的树脂组合物的制备：15g碱溶性光敏环氧丙烯酸树脂ZAR-1035(酸值100mgKOH/g，固含量64％)，2.5g丙烯酸酯单体(其中1.5g 20EOBPDMA、1.0g 10EOTMPTA)，0.5g光聚合引发剂(其中0.2g 184、0.3g 907)、0.05g光敏剂(ITX)，3.5g环氧树脂(其中1.8g萘环型低介电环氧树脂、0.9g NPES-901、0.8g增韧环氧树脂MX-154)， 0.01g三氟化硼乙胺潜伏型固化促进剂，0.3g炭黑MA-7，0.5g其他助剂(其中0.3g分散剂BYK168、0.1g流平剂BYK 394、0.1g消泡剂BYK354)，先经三辊研磨、然后高速搅拌溶解、分散，最后过滤制得胶液，暗光保存备用。
对比例3
一种用于高频高速印刷线路板的树脂组合物的制备：15g碱溶性光敏环氧丙烯酸树脂ZAR-1035(酸值100mgKOH/g，固含量64％)，2.5g丙烯酸酯单体(其中1.5g 20EOBPDMA、1.0g 10EOTMPTA)，0.5g光聚合引发剂(其中0.2g 184、0.3g 907)、0.05g光敏剂(ITX)，3.5g萘环型低介电环氧树脂，0.01g三氟化硼乙胺潜伏型固化促进剂，0.3g炭黑MA-7，0.5g其他助剂(其中0.3g分散剂BYK168、0.1g流平剂BYK 394、0.1g消泡剂BYK354)，先经三辊研磨、然后高速搅拌溶解、分散，最后过滤制得胶液，暗光保存备用。
潜伏型热固化促进剂和其他助剂未列入表1。
表1
Figure PCTCN2020100911-appb-000015
Figure PCTCN2020100911-appb-000016
*1：双酚A型含羧基环氧丙烯酸树脂ZAR-1035(Nippon Kayaku、酸值100mgKOH/g、固含量64％)
*2：丙烯酸树脂，n-BMA/EA/MMA/MAA/HEMA/STY(自己合成、酸值120mgKOH/g、分子量15w)
*3：氨基甲酸酯型含酸基树脂UXE-3000(Nippon Kayaku、酸值100mgKOH/g、固含量64％)
*4：20EOBPDMA为20乙氧基双酚A二甲基丙烯酸酯(沙多玛有限公司)
*5：10EOTMPTA为10乙氧基三羟甲基丙烷三丙烯酸酯(沙多玛有限公司)
*6：表层光引发剂，1-羟基环己基苯基甲酮(184)
*7：深层光引发剂，2-甲基-1-(4-甲硫基苯基)-2-吗啉-1-丙酮(907)
*8：光敏剂，2异丙基硫杂蒽酮(ITX)
*9：萘环型低介电环氧树脂，EBA-65(上海华谊树脂)
*10：环戊二烯型低介电环氧树脂，XD-1000(Nippon Kayaku)
*11：联苯型低介电环氧树脂，NC-3000(Nippon Kayaku)
*12：结晶性芴型环氧树脂，CG500(大阪瓦斯化学、环氧当量310g/eq)
*13：NPES-901(固体环氧树脂、南亚制造、环氧当量450-500g/eq)
*14：MX-154(核壳橡胶增韧环氧树脂、Kaneka、环氧当量301g/eq、聚丁二烯橡胶)
*15：炭黑MA-7(三菱化学、平均粒径24nm、pH值3.0、炉黑)
对所得的实施例及比较例用于高频高速印刷线路板的树脂组合物固化膜进行以下评价：
1、解像度
采用菲林片RP-4：um，L/S＝n/400对分辨率进行评价，显影后利用扫描电子显微镜(SEM)观察，以侧边形貌良好，完全显影清晰的最小线宽作为评价标准。
2、固化膜耐弯折性测试
将实施例和比较例中的固化膜进行180°角度对折测试，记录开始出现裂痕的次数并以下述基准进行评估。
◎：对折6次，固化膜上无裂痕
○：对折6次，固化膜固化膜上轻微裂痕
×：对折1次，固化膜断裂
3、锡焊耐热性的比较
参照IPC-TM650.2.6.8标准。固化膜垂直浸入温度300℃的锡炉浸泡3次，每次10s，观察表面是否起泡、变色、浮起和剥离等，以下述基准评估外观的变化。
◎：固化膜外观无变化
○：固化膜表面有变色
×：固化膜有浮起、薄离、锡焊深入
4、介电常数(Dk)和介电损耗(Df)的测量
将实施例和比较例中得到的固化膜在150℃干燥30min，在25℃及50％RH的条件下使用谐振器(安捷伦E5071BENA)通过分离介质谐振器(SPDR)方法测量各个树脂组合物在10GHz频率下的介电常数和介电损耗。
5、电绝缘性测试
固化膜在85℃、85％RH的恒温恒湿箱中静置24h后测试其表面电阻和体积电阻，测试条件为50V、1min。
◎：加湿后的绝缘电阻在10 9以上，无铜迁移
○：加湿后的绝缘电阻在10 9以上，有铜迁移
×：加湿后的绝缘电阻在10 9以下，有铜迁移
6、反弹力测试
参照环刚度测量法，将固化膜制成宽度10mm、周长60mm的测试圆环，记录使圆环沿径向压缩10mm所需的力，随后迅速撤掉外力，并记录圆环能恢复的径向高度，反弹力越小越好。
◎：反弹力＜40mN/mm
○：40≤反弹力＜50mN/mm
×：反弹力≥50mN/mm
表2固化膜性能测试比较
Figure PCTCN2020100911-appb-000017
Figure PCTCN2020100911-appb-000018
由表2可知，在感光性树脂组合物中添加低介电环氧树脂能提高固化膜的介电性能，显著降低介电常数和介电损耗因子，介电常数由3.5降至3.0以下，介电损耗因子由0.012降至0.008以下，满足了高频高速PCB和FPCB的要求，从而获得了兼具高解像度和优异介电性能的感光性阻焊保护层。同时，低介电环氧树脂特殊的分子结构也能进一步提高固化膜的耐热性并且对其反弹力影响较小，从而不会降低阻焊保护层的柔韧性和耐弯折性。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (12)

  1. 一种树脂组合物，其特征在于，按重量份计，所述树脂组合物包括100份的碱溶性树脂、5～30份的丙烯酸酯类单体、0.1～10份的光引发剂、10～30份的第一环氧树脂和0～15份的第二环氧树脂；其中所述第一环氧树脂为介电常数＜3.5的低介电环氧树脂，所述第二环氧树脂不同于所述第一环氧树脂。
  2. 根据权利要求1所述的树脂组合物，其特征在于，所述低介电环氧树脂为至少含有两个环氧基、环氧当量为160～2000g/eq的环氧树脂；优选地，所述低介电环氧树脂为联苯型环氧树脂、萘环型环氧树脂、萘酚型环氧树脂、亚萘基醚型环氧树脂、聚苯醚型环氧树脂、双环戊二烯型酚醛环氧树脂、结晶性芴型环氧树脂中的一种或多种，更优选为所述萘环型环氧树脂。
  3. 根据权利要求2所述的树脂组合物，其特征在于，
    所述联苯型环氧树脂具有式I所示结构：
    Figure PCTCN2020100911-appb-100001
    n为1～10的自然数；
    所述萘环型环氧树脂具有式II所示结构：
    Figure PCTCN2020100911-appb-100002
    n为1～10的自然数；
    所述萘酚型环氧树脂具有式III所示结构：
    Figure PCTCN2020100911-appb-100003
    n为1～10的自然数；
    所述亚萘基醚型环氧树脂具有式Ⅳ所示结构：
    Figure PCTCN2020100911-appb-100004
    所述聚苯醚型环氧树脂具有式Ⅴ所示结构：
    Figure PCTCN2020100911-appb-100005
    x和y分别为1～10的自然数；
    所述双环戊二烯型酚醛环氧树脂具有式Ⅵ所示结构：
    Figure PCTCN2020100911-appb-100006
    n为1～10的自然数；
    所述结晶性芴型环氧树脂具有式Ⅶ所示结构：
    Figure PCTCN2020100911-appb-100007
  4. 根据权利要求1至3中任一项所述的树脂组合物，其特征在于，所述碱溶性树脂的酸值为60～150mg KOH/g；
    优选地，所述碱溶性树脂选自感光性环氧丙烯酸树脂、苯丙烯树脂、感光性聚氨酯丙烯酸树脂中的一种或多种；
    优选地，所述感光性环氧丙烯酸树脂选自羧酸改性双酚A型环氧树脂、羧酸改性双酚F型环氧树脂、羧酸改性酚醛环氧树脂、羧酸改性邻甲酚醛环氧树脂中的一种或多种；
    优选地，所述苯丙烯树脂选自重均分子量为3～20w、玻璃化转变温度为90～150℃的羧酸改性苯丙烯酸树脂；
    优选地，所述感光性聚氨酯丙烯酸树脂选自脂肪族聚氨酯丙烯酸树脂、脂环族聚氨酯丙烯酸树脂、芳香族聚氨酯丙烯酸树脂中的一种或多种。
  5. 根据权利要求1至3中任一项所述的树脂组合物，其特征在于，所述丙烯酸酯类单体的重均分子量为200～2000，玻璃化转变温度为-20～100℃；
    优选地，所述丙烯酸酯类单体选自(乙氧基)苯酚(甲基)丙烯酸酯、硬脂酸丙烯酸酯、乙氧基(丙氧基)壬基苯酚(甲基)丙烯酸酯、乙氧基(丙氧基)四氢糠基(甲基)丙烯酸酯、1,6-己二醇二丙烯酸酯、PPG(400)二丙烯酸酯、三环葵烷二甲醇二丙烯酸酯、二氧杂环己烷二醇二丙烯酸酯、乙氧化(丙氧化)双酚A二(甲基)丙烯酸酯、聚乙二醇(400)二丙烯酸酯、聚丙二醇(600)二丙烯酸酯、乙氧基(丙氧基)三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇三丙烯酸酯、三(2-羟乙基)异氰尿酸三丙烯酸酯、 六丙烯酸二季戊四醇酯、乙氧基化季戊四醇四丙烯酸酯、双季戊四醇六丙烯酸酯中的一种或多种。
  6. 根据权利要求1至3中任一项所述的树脂组合物，其特征在于，所述光引发剂包括光聚合引发剂和光敏剂，且所述光聚合引发剂和所述光敏剂的重量比为2～20:1；
    优选地，所述光聚合引发剂选自1-羟基环己基苯基甲酮、2-羟基-2-甲基-1-苯基-1-丙酮、1-[4-(2-羟基)-苯基]-3-羟基-2-甲基-1-丙酮-1-酮、2-甲基-1-(4-甲硫基苯基)-2-吗啉-1-丙酮、2-苯基苄-2-二甲基胺-1-(4-吗啉苄苯基)丁酮、2,4,6-三甲基苯甲酰-二苯基氧化磷、双(2,4,6-三甲基苯甲酰基)苯基氧化膦、2,4,6-三甲基苯甲酰基苯基膦酸乙酯中的一种或多种；
    优选地，所述光敏剂选自2,4-乙二酸二乙酯、2-异丙基硫杂蒽酮、2,4-二乙基硫杂蒽酮、二苯甲酮、聚丁二醇双(9-氧代-9H-噻吨氧乙酸)酯中的一种或多种。
  7. 根据权利要求1至6中任一项所述的树脂组合物，其特征在于，按重量份计，所述树脂组合物还包括3～10份的增韧树脂；
    优选地，所述增韧树脂选自核壳橡胶增韧环氧树脂、热塑性弹性体、聚氨酯弹性体、液体橡胶、橡胶粉中的一种或多种。
  8. 根据权利要求7所述的树脂组合物，其特征在于，按重量份计，所述树脂组合物还包括0～5份的颜填料和0.01～5份的添加剂，所述添加剂选自热固化促进剂、分散剂、流平剂、消泡剂中的一种或多种；
    优选地，所述颜填料选自联苯胺黄、酞菁绿、酞菁蓝、炭黑、二氧化硅、硫酸钡、硫酸钙、滑石粉、水滑石中的一种多种；
    优选地，所述热固化促进剂为潜伏型热固化促进剂，更优选所述热固化促进剂选自三氟化硼乙胺络合物、己二酸二酰肼、对羟基安息香酸酰肼、间苯二甲酸酰肼、二胺基二苯砜、双氰胺及其衍生物中的一种或多种。
  9. 根据权利要求8所述的树脂组合物，其特征在于，按重量份计，所述树脂组合物包括100份的所述碱溶性树脂、5～30份的所述丙烯酸酯类单体、0.1～10份的所述光引发剂、10～30份的所述第一环氧树脂、0～15份的所述第二环氧树脂、5～7份的所述增韧树脂、1～5份的所述颜填料和1～5份的所述添加剂。
  10. 权利要求1至9中任一项所述的树脂组合物在高频高速印刷线路板领域的应用。
  11. 一种高频高速印刷线路板阻焊保护层的制备方法，其特征在于，包括以下步骤：
    将权利要求1至9中任一项所述的树脂组合物进行辊涂成膜，形成湿膜；
    将所述湿膜进行预烘干后，依次进行热辊贴膜、曝光、显影、热固化，得到所述阻焊保护层。
  12. 根据权利要求11所述的制备方法，其特征在于，所述湿膜的厚度为25～50μm；
    优选地，所述预烘干过程中，预烘干温度为80℃～100℃，时间为15～30min；
    优选地，所述曝光过程中的曝光能量为100～500mJ cm -2；
    优选地，所述显影过程中，采用的显影液为0.8～1.2wt％Na 2CO 3溶液，显影时间为30～60s，显影温度为27～33℃，喷淋压力为0.2～0.4MPa；
    优选地，所述热固化过程中，热固化温度为150～200℃，热固化时间为1～1.5h。
PCT/CN2020/100911 2019-08-28 2020-07-08 树脂组合物及其应用 WO2021036527A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP20856582.0A EP4024134A4 (en) 2019-08-28 2020-07-08 RESIN COMPOSITION AND USES THEREOF
US17/638,204 US20220308450A1 (en) 2019-08-28 2020-07-08 Resin composition and use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910804508.X 2019-08-28
CN201910804508.XA CN110554567B (zh) 2019-08-28 2019-08-28 树脂组合物及其应用

Publications (1)

Publication Number Publication Date
WO2021036527A1 true WO2021036527A1 (zh) 2021-03-04

Family

ID=68736719

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/100911 WO2021036527A1 (zh) 2019-08-28 2020-07-08 树脂组合物及其应用

Country Status (4)

Country Link
US (1) US20220308450A1 (zh)
EP (1) EP4024134A4 (zh)
CN (1) CN110554567B (zh)
WO (1) WO2021036527A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114716868A (zh) * 2022-04-19 2022-07-08 广州市红太电子科技有限公司 一种用于印刷电路板的光固化型油墨

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110554567B (zh) * 2019-08-28 2022-04-15 浙江福斯特新材料研究院有限公司 树脂组合物及其应用
CN111381440A (zh) * 2020-04-24 2020-07-07 浙江福斯特新材料研究院有限公司 感光覆盖膜组合物
CN112409756A (zh) * 2020-10-20 2021-02-26 中电科芜湖钻石飞机制造有限公司 低介电环氧树脂组合物及其制备方法、复合材料
CN112859518B (zh) * 2021-01-04 2024-04-19 赣州西琦光学科技有限公司 一种感光干膜及其制备方法
CN113604099A (zh) * 2021-07-08 2021-11-05 江苏海田电子材料有限公司 低介电常数阻焊油墨及其制备方法
CN113651920B (zh) * 2021-09-28 2023-06-06 泉州师范学院 基于丙烯酸液晶光敏树脂的组合物及其在405nm 3D打印中的应用
CN114058212A (zh) * 2021-11-18 2022-02-18 惠州市艾比森光电有限公司 黑色哑光油墨和pcb板及其制备方法
CN114539709B (zh) * 2022-03-11 2023-08-04 广东鸿翔瑞材料科技有限公司 树脂组合物、应用该树脂组合物的高分子膜及电路板
CN117004270B (zh) * 2023-08-10 2024-01-05 鹤山市炎墨科技有限公司 一种基于聚苯醚树脂的防焊油墨及其制备方法和应用

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4628022A (en) * 1983-07-13 1986-12-09 At&T Technologies, Inc. Multilayer circuit board fabrication process and polymer insulator used therein
CN108287451A (zh) 2018-01-24 2018-07-17 浙江福斯特新材料研究院有限公司 一种低介电感光覆盖膜树脂组合物
CN109270792A (zh) * 2018-10-30 2019-01-25 浙江福斯特新材料研究院有限公司 一种高韧性、高耐热、可弱碱水显影的聚酰亚胺/光敏环氧丙烯酸树脂组合物
CN109884859A (zh) * 2019-04-03 2019-06-14 浙江福斯特新材料研究院有限公司 一种高柔韧、高解析的光敏环氧丙烯酸树脂组合物
CN109923176A (zh) 2016-11-24 2019-06-21 纳美仕有限公司 树脂组合物、使用其的热固性膜、树脂固化物、层叠板、印刷电路板及半导体装置
CN110018613A (zh) * 2018-01-09 2019-07-16 味之素株式会社 树脂组合物
CN110554567A (zh) * 2019-08-28 2019-12-10 浙江福斯特新材料研究院有限公司 树脂组合物及其应用
CN111381440A (zh) * 2020-04-24 2020-07-07 浙江福斯特新材料研究院有限公司 感光覆盖膜组合物

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004018615A (ja) * 2002-06-14 2004-01-22 Sumitomo Bakelite Co Ltd 樹脂組成物、プリプレグ及び積層板
JP4033455B2 (ja) * 2002-11-07 2008-01-16 日本化薬株式会社 感光性樹脂組成物及びその硬化物
EP1600812A1 (en) * 2003-03-06 2005-11-30 Nippon Kayaku Kabushiki Kaisha Photosensitive resin composition and curing product thereof
JP6130693B2 (ja) * 2012-03-30 2017-05-17 太陽インキ製造株式会社 積層構造体、ドライフィルムおよび積層構造体の製造方法
JP6061576B2 (ja) * 2012-09-10 2017-01-18 株式会社タムラ製作所 感光性樹脂組成物及び感光性樹脂組成物の硬化被膜を有するプリント配線板
KR102207627B1 (ko) * 2013-03-07 2021-01-25 쇼와덴코머티리얼즈가부시끼가이샤 감광성 수지 조성물, 그것을 사용한 드라이 필름, 프린트 배선판, 및 프린트 배선판의 제조 방법
CN103694642B (zh) * 2013-12-27 2015-11-25 广东生益科技股份有限公司 一种热固性树脂组合物及其用途
CN105778412B (zh) * 2014-12-26 2018-05-29 广东生益科技股份有限公司 一种环氧树脂组合物以及使用它的预浸料和层压板
CN106318019B (zh) * 2015-07-06 2020-03-17 南亚塑胶工业股份有限公司 印刷电路板用低介电抗焊光阻油墨组合物
JP2017156590A (ja) * 2016-03-02 2017-09-07 太陽インキ製造株式会社 感光性樹脂組成物、ドライフィルム、硬化物およびそれを用いたプリント配線板
US10527936B2 (en) * 2016-06-17 2020-01-07 Nan Ya Plastics Corporation Low Dk/Df solder resistant composition use for printed circuit board
CN106939117B (zh) * 2017-04-17 2018-05-22 广州宏仁电子工业有限公司 树脂组合物及其应用
CN107450269B (zh) * 2017-08-11 2020-09-15 浙江福斯特新材料研究院有限公司 一种高韧性、可弱碱水显影的光敏环氧丙烯酸树脂组合物及其制备方法
JP7230508B2 (ja) * 2017-09-29 2023-03-01 東レ株式会社 感光性樹脂組成物、硬化膜、硬化膜を具備する有機ｅｌディスプレイ、並びに有機ｅｌディスプレイの製造方法
CN107942618B (zh) * 2017-11-29 2021-02-05 浙江福斯特新材料研究院有限公司 一种高粘附力速显影性干膜抗蚀剂

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4628022A (en) * 1983-07-13 1986-12-09 At&T Technologies, Inc. Multilayer circuit board fabrication process and polymer insulator used therein
CN109923176A (zh) 2016-11-24 2019-06-21 纳美仕有限公司 树脂组合物、使用其的热固性膜、树脂固化物、层叠板、印刷电路板及半导体装置
CN110018613A (zh) * 2018-01-09 2019-07-16 味之素株式会社 树脂组合物
CN108287451A (zh) 2018-01-24 2018-07-17 浙江福斯特新材料研究院有限公司 一种低介电感光覆盖膜树脂组合物
CN109270792A (zh) * 2018-10-30 2019-01-25 浙江福斯特新材料研究院有限公司 一种高韧性、高耐热、可弱碱水显影的聚酰亚胺/光敏环氧丙烯酸树脂组合物
CN109884859A (zh) * 2019-04-03 2019-06-14 浙江福斯特新材料研究院有限公司 一种高柔韧、高解析的光敏环氧丙烯酸树脂组合物
CN110554567A (zh) * 2019-08-28 2019-12-10 浙江福斯特新材料研究院有限公司 树脂组合物及其应用
CN111381440A (zh) * 2020-04-24 2020-07-07 浙江福斯特新材料研究院有限公司 感光覆盖膜组合物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114716868A (zh) * 2022-04-19 2022-07-08 广州市红太电子科技有限公司 一种用于印刷电路板的光固化型油墨
CN114716868B (zh) * 2022-04-19 2023-06-20 广州市红太电子科技有限公司 一种用于印刷电路板的光固化型油墨

Also Published As

Publication number Publication date
CN110554567B (zh) 2022-04-15
CN110554567A (zh) 2019-12-10
US20220308450A1 (en) 2022-09-29
EP4024134A1 (en) 2022-07-06
EP4024134A4 (en) 2023-10-25

Similar Documents

Publication Publication Date Title
WO2021036527A1 (zh) 树脂组合物及其应用
CN106814538B (zh) 固化性树脂组合物、干膜、固化物和印刷电路板
KR101631059B1 (ko) 컬러 레지스트 조성물 및 이 조성물을 이용한 컬러 필터
CN107272334B (zh) 固化性树脂组合物、干膜、固化物和印刷电路板
JP5090210B2 (ja) 活性エネルギー線硬化性樹脂及びその製造方法
US20130260109A1 (en) Photocurable resin composition, dry film, cured product and printed wiring board
KR100928762B1 (ko) 착색 감광성 수지 조성물
KR101758690B1 (ko) 경화성 수지 조성물, 컬러 필터, 화상 표시 소자 및 컬러 필터의 제조 방법
JP5843907B2 (ja) 着色感光性樹脂組成物、ブラックマトリックス、カラーフィルター、及び液晶表示ディスプレイ
US20080097000A1 (en) Photosensitive resin composition for flexible circuit board and flexible circuit board using the same
JP4768924B2 (ja) フォトソルダーレジストインク
JP4532002B2 (ja) ソルダーレジストインク
TW202237676A (zh) 共聚物及該共聚物之製造方法
WO2001055790A1 (fr) Compositions de resine photodurcissable
JP4949809B2 (ja) 着色感光性樹脂組成物
CN117551259A (zh) 环氧树脂组合物及改性环氧树脂、碱溶性聚氨酯树脂组合物及碱溶性聚氨酯树脂、阻焊剂
WO2020021717A1 (ja) ドライレジストフィルム、ソルダーレジスト、電磁波シールドシート付きプリント配線板およびその製造方法、並びに電子機器
CN112940560B (zh) 感光阻焊油墨组合物、其用途以及含有其的线路板
CN112925168A (zh) 一种氧化石墨烯增强感光覆盖膜组合物
CN115677939A (zh) 一种感光性接枝聚合物以及含有其的感光性树脂组合物
JP2020047654A (ja) 硬化性樹脂組成物、ドライフィルム、硬化物およびプリント配線板
CN112711175A (zh) 一种黑色固化性树脂组合物
KR20210148171A (ko) 경화성 수지 조성물, 드라이 필름, 경화물 및 전자 부품
JP5858747B2 (ja) 新規な感光性樹脂組成物作製キット及びその利用
KR20170080680A (ko) 연성 인쇄 회로 기판을 위한 광이미지형성 커버레이 조성물

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20856582

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2020856582

Country of ref document: EP

Effective date: 20220328