WO2021109442A1 - 改性炭黑及其制备方法、树脂组合物、覆铜板 - Google Patents

改性炭黑及其制备方法、树脂组合物、覆铜板 Download PDF

Info

Publication number
WO2021109442A1
WO2021109442A1 PCT/CN2020/088414 CN2020088414W WO2021109442A1 WO 2021109442 A1 WO2021109442 A1 WO 2021109442A1 CN 2020088414 W CN2020088414 W CN 2020088414W WO 2021109442 A1 WO2021109442 A1 WO 2021109442A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon black
modified
modified carbon
parts
resin composition
Prior art date
Application number
PCT/CN2020/088414
Other languages
English (en)
French (fr)
Inventor
郭永军
温文彦
漆小龙
朱扬杰
Original Assignee
广东盈骅新材料科技有限公司
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 广东盈骅新材料科技有限公司 filed Critical 广东盈骅新材料科技有限公司
Priority to US17/627,083 priority Critical patent/US20220267608A1/en
Priority to JP2022502505A priority patent/JP7457787B2/ja
Priority to KR1020227018460A priority patent/KR20220092582A/ko
Publication of WO2021109442A1 publication Critical patent/WO2021109442A1/zh

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/56—Treatment of carbon black ; Purification
    • C09C1/565—Treatment of carbon black ; Purification comprising an oxidative treatment with oxygen, ozone or oxygenated compounds, e.g. when such treatment occurs in a region of the furnace next to the carbon black generating reaction zone
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
    • B32B17/04—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • 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
    • H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/107—Ceramic
    • B32B2264/108—Carbon, e.g. graphite particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/07—Parts immersed or impregnated in a matrix
    • B32B2305/076—Prepregs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/41—Opaque
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • 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
    • H05K1/0274—Optical details, e.g. printed circuits comprising integral optical means
    • 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
    • H05K2201/03—Conductive materials
    • H05K2201/032—Materials
    • H05K2201/0323—Carbon

Definitions

  • the invention relates to the technical field of materials, in particular to a modified carbon black, a preparation method thereof, a resin composition, and a copper clad laminate.
  • carbon black is often added to the copper-clad laminates in the industry to give the plate a black function, thereby achieving the purpose of shading.
  • carbon black due to the small particle size, large specific surface area, and easy agglomeration of carbon black particles, it is difficult to stably disperse in various media.
  • carbon black has electrical conductivity and easily affects the insulation performance of the material. These defects limit the performance of carbon black. fully use.
  • CN201010177757 uses a small amount of carbon black powder to make the resin composition black and has a light-shielding effect, and uses titanium dioxide to enhance the light-shielding effect to obtain a black covering film, but the direct addition of carbon black powder will cause the insulation performance of the material to decrease.
  • CN201310425929 adds graphene or graphene oxide coated inorganic fillers, without reducing the insulation of the prepared copper-clad substrate, greatly reducing the light transmittance of the prepared copper-clad substrate, but the price of graphene is relatively high High and high cost.
  • the present invention provides a modified carbon black, which not only imparts good light-shielding characteristics to the copper clad laminate, does not affect the insulation performance of the copper clad laminate, has good dispersibility and low cost.
  • a modified carbon black including carbon black and modified groups
  • the surface of the carbon black has an acid chloride group; the modified group is formed by reacting and grafting a modified polymer with the acid chloride group; the modified polymer is an alcohol polymer.
  • the particle size of the carbon black is 5-100 nm.
  • the particle size of the carbon black is 5-50 nm.
  • the present invention also provides a method for preparing modified carbon black, which includes the following steps:
  • the modified polymer is selected from alcohol polymers.
  • the particle size of the carbon black is 5-100 nm.
  • the particle size of the carbon black is 5-50 nm.
  • the surface oxidation modification includes the following steps:
  • the oxidant and the carbon black are mixed and reacted at 20-30°C; then the solid obtained by the reaction is washed with water and dried.
  • the oxidant is any one of nitric acid, hydrogen peroxide and ammonium persulfate.
  • the reaction time is 1.5-2.5h;
  • reaction time is 95-97h
  • the reaction time is 23-25h.
  • the method of acyl chlorination is: mixing the carbon black after surface oxidation modification with thionyl chloride in a solvent, and reacting at 35-45°C. ⁇ 12h.
  • step (2) the grafting reaction includes the following steps:
  • the carbon black with an acid chloride group formed on the surface and the modified polymer are mixed, and reacted at 50-90° C. for 10-30 hours.
  • the present invention also provides a resin composition comprising the modified carbon black as described above or the modified carbon black prepared by the preparation method as described above.
  • the resin composition is prepared from raw materials including the following components in terms of weight percentage:
  • the present invention also provides a copper clad laminate, which uses the resin composition as described above.
  • the present invention has the following beneficial effects:
  • the modified carbon black of the present invention is grafted with a modified polymer on the surface of the modified carbon black to form a modified group, wherein the modified polymer is an alcohol polymer, which can be modified Reactive carbon black has excellent insulating properties, while the van der Waals force between particles is small, and can be stably dispersed in the medium.
  • the copper clad laminate prepared by it has excellent insulating properties and light-shielding properties, and the preparation cost is low.
  • the embodiment of the present invention provides a modified carbon black, including carbon black and a modified group
  • the surface of the carbon black has an acid chloride group; the modified group is formed by reacting and grafting a modified polymer with the acid chloride group, and the modified polymer is an alcohol polymer.
  • the alcohol polymer is polyethylene glycol or polypropylene glycol
  • the particle size of the carbon black is 5-100 nm.
  • the particle size of the carbon black is 5-50 nm.
  • the use of carbon black in this particle size range can provide even better light-shielding performance.
  • the embodiment of the present invention also provides a method for preparing the above modified carbon black, which includes the following steps:
  • the modified polymer is an alcohol polymer.
  • the acid chloride group reacts with alcohols to form esters and hydrogen chloride.
  • the surface oxidation modification includes the following steps: mixing an oxidizing agent and the carbon black, and reacting at 20-30°C; and then washing the solid obtained by the reaction with water ,dry.
  • the oxidant is any one of nitric acid, hydrogen peroxide and ammonium persulfate.
  • the hydrogen peroxide can be an aqueous hydrogen peroxide solution with a mass concentration of 0.3-1.0%
  • the ammonium persulfate can be a saturated ammonium persulfate solution.
  • the reaction time when the oxidant is nitric acid, the reaction time is 1.5-2.5h; when the oxidant is hydrogen peroxide, the reaction time is 95-97h; When the oxidant is ammonium persulfate, the reaction time is 23-25h.
  • the oxidation time is reasonably controlled so that the carbon black and the oxidant can fully react, the content of oxygen-containing groups on the surface of the modified carbon black is significantly increased, and the oxidant will not leave other substances in the modified carbon black.
  • the drying method is: drying under vacuum conditions at a temperature of 110-130° C. and a pressure of 0.2-0.4 kPa.
  • the method of acyl chlorination is: mixing the surface oxidation-modified carbon black with thionyl chloride in a solvent at 35-45°C
  • the reaction time is 8-12h.
  • the solvent is dichloroethane.
  • post-treatment is performed: firstly, the solvent is evaporated under reduced pressure, and then the temperature is raised to 50° C., and vacuum is applied to remove the remaining thionyl chloride.
  • step (2) the grafting reaction includes the following steps:
  • the carbon black with an acid chloride group formed on the surface and the modified polymer are mixed, and reacted at 50-90° C. for 10-30 hours.
  • the solvent is dichloroethane.
  • post-treatment is performed: the obtained solid is washed with water, and dried at 100-120°C for 22-25h.
  • the embodiment of the present invention also provides a resin composition, including the modified carbon black as described above or the modified carbon black prepared by the preparation method as described above.
  • the resin composition is prepared from raw materials including the following components in terms of weight percentage:
  • the functional resin is an epoxy resin, including but not limited to cycloaliphatic epoxy resin, bisphenol A epoxy resin, o-cresol epoxy resin, phosphorus-containing epoxy resin, phenol novolac epoxy resin, Benzene type epoxy resin, naphthalene ring type epoxy resin, etc.; bismaleimide, including but not limited to diphenylmethane bismaleimide, N ⁇ -m-phenylene bismaleimide, polyamine Benzoxazine, including but not limited to bisphenol A type benzoxazine, MDA type benzoxazine, phenol type benzoxazine, DCPD benzoxazine, etc.;
  • the curing agent includes, but is not limited to, cyanate ester curing agent, aliphatic polyamine curing agent, alicyclic polyamine curing agent, aromatic amine curing agent, polyamide curing agent, latent curing agent, Lewis Acid-amine complex curing agent, acid anhydride curing agent, phenolic curing agent, etc.
  • the filler includes, but is not limited to, titanium dioxide, silicon dioxide, magnesium oxide, magnesium hydroxide, talc, mica powder, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, and the like.
  • the coupling agent includes, but is not limited to, a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, an organic chromium complex coupling agent, and the like.
  • the curing accelerator includes, but is not limited to, imidazole accelerators, peroxide accelerators, azo accelerators, tertiary amine accelerators, phenol accelerators, organic metal salt accelerators, and inorganic metal salts Promoter, etc.
  • the present invention also provides a copper clad laminate, which uses the resin composition as described above.
  • the carbon black used in the examples has a particle size of 5-50 nm.
  • the 2116 glass fiber cloth (basis weight 105g/m 2 ) was impregnated with this glue, and baked in a hot-air circulating oven at 180°C for 3 minutes to obtain a prepreg with a resin content of 55%.
  • the four superimposed prepregs, an electrolytic copper foil in the laminate cover each upper and lower surfaces of a thickness of 12 ⁇ m, the program may be placed in a vacuum press for controlling temperature and pressure in a vacuum state, at 25kgf / cm 2 of Under pressure conditions, the product temperature was cured at 200°C for 100 minutes to produce a copper clad laminate with a thickness of 0.4mm.
  • the 2116 glass fiber cloth (basis weight 105g/m 2 ) was impregnated with this glue, and baked in a hot air circulating oven at 180°C for 3 minutes to obtain a prepreg with a resin content of 45%.
  • the four superimposed prepregs, an electrolytic copper foil in the laminate cover each upper and lower surfaces of a thickness of 12 ⁇ m, the program may be placed in a vacuum press for controlling temperature and pressure in a vacuum state, at 25kgf / cm 2 of Under pressure conditions, the product temperature was cured at 200°C for 100 minutes to produce a copper clad laminate with a thickness of 0.4mm.
  • the 2116 glass fiber cloth (basis weight 105g/m 2 ) was impregnated with this glue, and baked in a hot air circulating oven at 180°C for 3 minutes to obtain a prepreg with a resin content of 50%.
  • the four superimposed prepregs, an electrolytic copper foil in the laminate cover each upper and lower surfaces of a thickness of 12 ⁇ m, the program may be placed in a vacuum press for controlling temperature and pressure in a vacuum state, at 25kgf / cm 2 of Under pressure conditions, the product temperature was cured at 200°C for 100 minutes to produce a copper clad laminate with a thickness of 0.4mm.
  • the 2116 glass fiber cloth (basis weight 105g/m 2 ) was impregnated with this glue, and baked in a hot-air circulating oven at 180°C for 3 minutes to obtain a prepreg with a resin content of 55%.
  • the four superimposed prepregs, an electrolytic copper foil in the laminate cover each upper and lower surfaces of a thickness of 12 ⁇ m, the program may be placed in a vacuum press for controlling temperature and pressure in a vacuum state, at 25kgf / cm 2 of Under pressure conditions, the product temperature was cured at 200°C for 100 minutes to produce a copper clad laminate with a thickness of 0.4mm.
  • the 2116 glass fiber cloth (basis weight 105g/m 2 ) was impregnated with this glue, and baked in a hot-air circulating oven at 180°C for 3 minutes to obtain a prepreg with a resin content of 55%.
  • the four superimposed prepregs, an electrolytic copper foil in the laminate cover each upper and lower surfaces of a thickness of 12 ⁇ m, the program may be placed in a vacuum press for controlling temperature and pressure in a vacuum state, at 25kgf / cm 2 of Under pressure conditions, the product temperature was cured at 200°C for 100 minutes to produce a copper clad laminate with a thickness of 0.4mm.
  • the 2116 glass fiber cloth (basis weight 105g/m 2 ) was impregnated with this glue, and baked in a hot-air circulating oven at 180°C for 3 minutes to obtain a prepreg with a resin content of 55%.
  • the four superimposed prepregs, an electrolytic copper foil in the laminate cover each upper and lower surfaces of a thickness of 12 ⁇ m, the program may be placed in a vacuum press for controlling temperature and pressure in a vacuum state, at 25kgf / cm 2 of Under pressure conditions, the product temperature was cured at 200°C for 100 minutes to produce a copper clad laminate with a thickness of 0.4mm.
  • the 2116 glass fiber cloth (basis weight 105g/m 2 ) was impregnated with this glue, and baked in a hot-air circulating oven at 180°C for 3 minutes to obtain a prepreg with a resin content of 55%.
  • the four superimposed prepregs, an electrolytic copper foil in the laminate cover each upper and lower surfaces of a thickness of 12 ⁇ m, the program may be placed in a vacuum press for controlling temperature and pressure in a vacuum state, at 25kgf / cm 2 of Under pressure conditions, the product temperature was cured at 200°C for 100 minutes to produce a copper clad laminate with a thickness of 0.4mm.
  • the 2116 glass fiber cloth (basis weight 105g/m 2 ) was impregnated with this glue, and baked in a hot-air circulating oven at 180°C for 3 minutes to obtain a prepreg with a resin content of 55%.
  • the four superimposed prepregs, an electrolytic copper foil in the laminate cover each upper and lower surfaces of a thickness of 12 ⁇ m, the program may be placed in a vacuum press for controlling temperature and pressure in a vacuum state, at 25kgf / cm 2 of Under pressure conditions, the product temperature was cured at 200°C for 100 minutes to produce a copper clad laminate with a thickness of 0.4mm.
  • Light transmittance use a light transmittance tester to test
  • Dispersibility The aqueous solutions of modified carbon black and unmodified carbon black were tested for light transmittance before and after centrifugation for 60 minutes in a centrifuge. The greater the difference in light transmittance before and after centrifugation, the more uneven the dispersion, that is, the worse the dispersion.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Polyethers (AREA)

Abstract

本发明涉及一种改性炭黑及其制备方法、树脂组合物、覆铜板。所述改性炭黑包括炭黑以及改性基团；所述炭黑的表面具有酰氯基团；所述改性基团由改性高分子与所述酰氯基团反应接枝而成；所述改性高分子为醇类高分子。所述改性炭黑在赋予覆铜板以良好遮光特性的同时，不影响覆铜板的绝缘性能，分散性好，成本低。

Description

改性炭黑及其制备方法、树脂组合物、覆铜板 技术领域
本发明涉及材料技术领域，特别是涉及一种改性炭黑及其制备方法、树脂组合物、覆铜板。
背景技术
近年来，由于LED(发光二极管：Light-Emitting Diode)的低能耗、高效率的突出特点，已被广泛应用于电器指示、高清LED显示屏、LED背光源、景观照明、室内装饰等领域。由于LED的高速发展，也推动了功能性覆铜板的发展。之所以称之为功能性覆铜板，那是因为用于LED的覆铜板除了需要具备普通覆铜板所具有的绝缘等性能以外，还需要具有良好的遮光功能，以应尽可能地避免LED光源的光线从板材背面透过，以及很好的吸收外界自然光，从而提高LED显示屏的清晰度和分辨度。
为了赋予覆铜板以遮光特性，目前业界较常使用炭黑添加到覆铜板中以赋予板材黑色功能，进而达到遮光的目的。但是由于碳黑粒子粒度小、比表面积大、易团聚等特性，很难稳定分散在各种介质中，同时，炭黑具有导电性，容易影响材料的绝缘性能，这些缺陷限制了炭黑性能的充分发挥。
CN201010177757采用少量炭黑粉使树脂组合物成为黑色及起遮光作用，采用二氧化钛起增强遮光作用，得到一种黑色覆盖膜，但直接添加炭黑粉会引起材料绝缘性能下降。
CN201310425929通过加入石墨烯或氧化石墨烯包覆处理的无机填料，在不降低制备的覆铜箔基板的绝缘性的前提下，大大降低了制备的覆铜箔基板透光 率，但是石墨烯价格较高，成本高。
发明内容
基于此，本发明提供一种改性炭黑，其在赋予覆铜板以良好遮光特性的同时，不影响覆铜板的绝缘性能，分散性好，成本低。
一种改性炭黑，包括炭黑以及改性基团；
所述炭黑的表面具有酰氯基团；所述改性基团由改性高分子与所述酰氯基团反应接枝而成；所述改性高分子为醇类高分子。
在其中一个实施例中，所述炭黑的粒径为5～100nm。
在其中一个实施例中，所述炭黑的粒径为5～50nm。
本发明还提供一种改性炭黑的制备方法，包括如下步骤：
(1)通过液相法对炭黑进行表面氧化改性，然后酰氯化，以在所述炭黑的表面形成酰氯基团；
(2)混合所述表面形成有酰氯基团的炭黑和改性高分子，进行接枝反应以形成改性基团；所述改性高分子选自醇类高分子。
在其中一个实施例中，所述炭黑的粒径为5～100nm。
在其中一个实施例中，所述炭黑的粒径为5～50nm。
在其中一个实施例中，步骤(1)中，所述表面氧化改性包括如下步骤：
将氧化剂和所述炭黑混合，在20～30℃下反应；然后用水对反应所得固体进行清洗，干燥。
在其中一个实施例中，所述氧化剂为硝酸、过氧化氢和过硫酸铵中的任意一种。
在其中一个实施例中，当所述氧化剂为硝酸时，所述反应的时间为1.5～2.5h；
当所述氧化剂为过氧化氢时，所述反应的时间为95～97h；
当所述氧化剂为过硫酸铵时，所述反应的时间为23～25h。
在其中一个实施例中，步骤(1)中，所述酰氯化的方法为：于溶剂中，将所述表面氧化改性后的炭黑与二氯亚砜混合，于35～45℃反应8～12h。
在其中一个实施例中，步骤(2)中，所述接枝反应包括如下步骤：
于溶剂中，混合所述表面形成有酰氯基团的炭黑和改性高分子，于50～90℃反应10～30h。
本发明还提供一种树脂组合物，包括如上所述的改性炭黑或如上所述的制备方法制备得到的改性炭黑。
在其中一个实施例中，所述的树脂组合物，以重量百分比计，由包括如下组分的原料制备而成：
Figure PCTCN2020088414-appb-000001
本发明还提供一种覆铜板，其采用的胶料为如上所述的树脂组合物。
与现有方案相比，本发明具有以下有益效果：
本发明所述的改性炭黑，经过其表面的酰氯基团与改性高分子进行接枝形成改性基团，其中，所述改性高分子为醇类高分子，由此可使改性炭黑具有优异的绝缘性，同时粒子间的范德华力较小，可以稳定地分散于介质中，采用其制备而成的覆铜板兼具优异的绝缘性能和遮光性能，且制备成本低。
具体实施方式
以下结合具体实施例对本发明作进一步详细的说明。本发明可以以许多不同的形式来实现，并不限于本文所描述的实施方式。相反地，提供这些实施方式的目的是使对本发明公开内容理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。
本发明的实施例提供一种改性炭黑，包括炭黑以及改性基团；
所述炭黑的表面具有酰氯基团；所述改性基团由改性高分子与所述酰氯基团反应接枝而成，所述改性高分子为醇类高分子。
在其中一个具体的实施例中，所述醇类高分子为聚乙二醇或聚丙二醇；
在其中一个具体的实施例中，所述炭黑的粒径为5～100nm。作为优选地，所述炭黑的粒径为5～50nm。采用该粒径范围的炭黑，能够具备更加优秀的遮光性能。
本发明的实施例还提供上述改性炭黑的制备方法，包括如下步骤：
(1)通过液相法对炭黑进行表面氧化改性，然后酰氯化，以在所述炭黑的表面形成酰氯基团；
(2)混合所述表面形成有酰氯基团的炭黑和改性高分子，进行接枝反应以形成改性基团；所述改性高分子为醇类高分子。
可以理解地，当与醇类高分子反应时，酰氯基团与醇类反应生成酯类和氯化氢。
在其中一个具体的实施例中，步骤(1)中，所述表面氧化改性包括如下步 骤：将氧化剂和所述炭黑混合，在20～30℃下反应；然后用水对反应所得固体进行清洗，干燥。
在其中一个具体的实施例中，所述氧化剂为硝酸、过氧化氢和过硫酸铵中的任意一种。具体地，所述过氧化氢可采用质量浓度0.3～1.0％的过氧化氢水溶液，所述过硫酸铵可采用饱和过硫酸铵溶液。
在其中一个具体的实施例中，当所述氧化剂为硝酸时，所述反应的时间为1.5～2.5h；当所述氧化剂为过氧化氢时，所述反应的时间为95～97h；当所述氧化剂为过硫酸铵时，所述反应的时间为23～25h。对氧化时间进行合理控制，使得炭黑与氧化剂之间可以充分反应，改性后的炭黑表面含氧基团含量明显增大，且氧化剂不会在改性后的炭黑中残留其它物质。
在其中一个具体的实施例中，所述干燥的方式为：在温度为110～130℃、压力为0.2～0.4kPa的真空条件下干燥。
在其中一个具体的实施例中，步骤(1)中，所述酰氯化的方法为：于溶剂中，将所述表面氧化改性后的炭黑与二氯亚砜混合，于35～45℃反应8～12h。
在其中一个具体的实施例中，所述溶剂为二氯乙烷。
在其中一个具体的实施例中，反应完成后，进行后处理：先减压蒸出溶剂，然后升温至50℃，抽真空以脱出残存的二氯亚砜。
在其中一个具体的实施例中，步骤(2)中，所述接枝反应包括如下步骤：
于溶剂中，混合所述表面形成有酰氯基团的炭黑和改性高分子，于50～90℃反应10～30h。
在其中一个具体的实施例中，所述溶剂为二氯乙烷。
在其中一个具体的实施例中，反应完成后，进行后处理：将所得固体用水清洗后，于100～120℃干燥22～25h。
本发明的实施例还提供一种树脂组合物，包括如上所述的改性炭黑或如上所述的制备方法制备得到的改性炭黑。
在其中一个实施例中，所述的树脂组合物以重量百分比计，由包括如下组分的原料制备而成：
Figure PCTCN2020088414-appb-000002
具体地，所述功能树脂为环氧树脂，包括但不限于脂环族环氧树脂、双酚A环氧树脂、邻甲酚醛环氧树脂、含磷环氧树脂、苯酚酚醛环氧树脂、联苯型环氧树脂、萘环型环氧树脂等；双马来酰亚胺，包括但不限于二苯甲烷双马来酰亚胺、N`-间苯撑双马来酰亚胺、聚胺基双马来酰亚胺等；苯并噁嗪，包括但不限于双酚A型苯并噁嗪、MDA型苯并噁嗪、苯酚型苯并噁嗪、DCPD苯并噁嗪等。
具体地，所述固化剂包括但不限于氰酸酯固化剂、脂肪多元胺型固化剂、脂环多元胺型固化剂、芳香胺类固化剂、聚酰胺类型固化剂、潜伏型固化剂、路易斯酸-胺络合物类固化剂、酸酐类固化剂、酚醛型固化剂等。
具体地，所述填料包括但不限于二氧化钛、二氧化硅、氧化镁、氢氧化镁、滑石粉、云母粉、氧化铝、碳化硅、氮化硼、氮化铝、氧化钼和硫酸钡等。
具体地，所述偶联剂包括但不限于硅烷类偶联剂、钛酸酯偶联剂、铝酸酯偶联剂和有机铬络合物偶联剂等。
具体地，所述固化促进剂包括但不限于咪唑类促进剂、过氧化物类促进剂、偶氮类促进剂、叔胺类促进剂、酚类促进剂、有机金属盐促进剂和无机金属盐促进剂等。
本发明还提供一种覆铜板，其采用的胶料为如上所述树脂组合物。
如下为具体的实施例，如无特别说明所采用的原料均为市售产品。
实施例中采用的炭黑的粒径均为5～50nm。
改性炭黑1的制备：
(1)将100ml的硝酸和10g的炭黑混合，在25℃下反应2h。反应完毕后过滤，用去离子水清洗，直到清洗液的pH值恒定后，将炭黑在温度为120℃、压力为0.3kPa的真空烘箱中烘至恒质量后密闭、干燥贮存后得到表面氧化炭黑。
(2)分别将10g上述表面氧化炭黑、6ml的二氯亚砜和200ml的二氯乙烷加入三口烧瓶中，升温至40℃并且搅拌反应10h，待反应结束后减压蒸出二氯乙烷溶剂，升温至50℃，抽真空以脱出残存的二氯亚砜，即得表面酰氯化活性炭黑。
(3)分别将5g的活化炭黑、3g的聚乙二醇和200ml的二氯乙烷加入三口烧瓶搅拌，在50℃下反应30h，反应结束后减压蒸出二氯乙烷溶剂后将接枝炭黑用去离子水反复洗涤后用110℃干燥24h。
改性炭黑2的制备：
(1)将100ml的饱和过硫酸铵溶液和10g的炭黑混合，在25℃下反应24h。反应完毕后过滤，用去离子水清洗，直到清洗液的pH值恒定后，将炭黑在温度为120℃、压力为0.3kPa的真空烘箱中烘至恒质量后密闭、干燥贮存后得到表 面氧化炭黑。
(2)分别将上述10g的表面氧化炭黑、6ml的二氯亚砜和200ml的二氯乙烷加入三口烧瓶中，升温至40℃并且搅拌反应10h，待反应结束后减压蒸出二氯乙烷溶剂，升温至50℃，抽真空以脱出残存的二氯亚砜，即得表面酰氯化活性炭黑。
(3)分别将5g的活化炭黑、3g的聚乙二醇和200ml的二氯乙烷溶液加入三口烧瓶搅拌，在90℃下反应10h，反应结束后减压蒸出二氯乙烷溶剂后将接枝炭黑用去离子水反复洗涤后用110℃干燥24h。
改性炭黑3的制备：
(1)将100ml的过氧化氢溶液和10g的炭黑混合，在25℃下反应96h。反应完毕后过滤，用去离子水清洗，直到清洗液的pH值恒定后，将炭黑在温度为120℃、压力为0.3kPa的真空烘箱中烘至恒质量后密闭、干燥贮存后得到表面氧化炭黑。
(2)分别将10g的上述表面氧化炭黑、6ml的二氯亚砜和200ml的二氯乙烷加入三口烧瓶中，升温至40℃并且搅拌反应10h，待反应结束后减压蒸出二氯乙烷溶剂，升温至50℃，抽真空以脱出残存的二氯亚砜，即得表面酰氯化活性炭黑。
(3)分别将5g的活化炭黑、3g的聚乙二醇和200ml的二氯乙烷溶液加入三口烧瓶搅拌，在70℃下反应20h，反应结束后减压蒸出二氯乙烷溶剂后将接枝炭黑用去离子水反复洗涤后用110℃干燥24h。
实施例1：
依次将5份的改性炭黑1、70份双酚A环氧树脂、30份的酚醛型固化剂溶于按质量比1:1:1配比的丁酮、甲苯、丙二醇甲醚混合溶剂中后，于搅拌条件下加入25份的氧化铝、35份的二氧化硅、2份的硅烷偶联剂和2份的2-甲基咪唑后继续搅拌均匀制备成胶液。
用此胶液浸渍2116玻璃纤维布(基重105g/m 2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为55％的预浸料。将4片预浸料重叠，在该层叠体上下两面各覆盖一张厚度为12μm的电解铜箔，置于可程式控温控压的真空压机中，在真空状态，在25kgf/cm 2的压力条件，制品温度在200℃条件下固化100分钟，制成0.4mm厚度的覆铜箔层压板。
实施例2：
依次将5份的改性炭黑1、30份苯并噁嗪树脂、2份的酚醛型固化剂溶于按质量比1:1:1配比的丁酮、甲苯、丙二醇甲醚混合溶剂中后，于搅拌条件下加入10份的氧化铝、10份的二氧化硅、0.1份的硅烷偶联剂和0.1份的2-甲基咪唑后继续搅拌均匀制备成胶液。
用此胶液浸渍2116玻璃纤维布(基重105g/m 2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为45％的预浸料。将4片预浸料重叠，在该层叠体上下两面各覆盖一张厚度为12μm的电解铜箔，置于可程式控温控压的真空压机中，在真空状态，在25kgf/cm 2的压力条件，制品温度在200℃条件下固化100分钟，制成0.4mm厚度的覆铜箔层压板。
实施例3：
依次将0.1份的改性炭黑1、50份双酚A环氧树脂、15份的酚醛型固化剂 溶于按质量比1:1:1配比的丁酮、甲苯、丙二醇甲醚混合溶剂中后，于搅拌条件下加入25份的氧化铝、15份的二氧化硅、1份的硅烷偶联剂和1份的2-甲基咪唑后继续搅拌均匀制备成胶液。
用此胶液浸渍2116玻璃纤维布(基重105g/m 2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为50％的预浸料。将4片预浸料重叠，在该层叠体上下两面各覆盖一张厚度为12μm的电解铜箔，置于可程式控温控压的真空压机中，在真空状态，在25kgf/cm 2的压力条件，制品温度在200℃条件下固化100分钟，制成0.4mm厚度的覆铜箔层压板。
实施例4：
依次将10份的改性炭黑1、70份双酚A环氧树脂、30份的酚醛型固化剂溶于按质量比1:1:1配比的丁酮、甲苯、丙二醇甲醚混合溶剂中后，于搅拌条件下加入25份的氧化铝、35份的二氧化硅、2份的硅烷偶联剂和2份的2-甲基咪唑后继续搅拌均匀制备成胶液。
用此胶液浸渍2116玻璃纤维布(基重105g/m 2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为55％的预浸料。将4片预浸料重叠，在该层叠体上下两面各覆盖一张厚度为12μm的电解铜箔，置于可程式控温控压的真空压机中，在真空状态，在25kgf/cm 2的压力条件，制品温度在200℃条件下固化100分钟，制成0.4mm厚度的覆铜箔层压板。
实施例5：
依次将5份的改性炭黑2、70份双酚A环氧树脂、30份的酚醛型固化剂溶于按质量比1:1:1配比的丁酮、甲苯、丙二醇甲醚混合溶剂中后，于搅拌条件下 加入25份的氧化铝、35份的二氧化硅、2份的硅烷偶联剂和2份的2-甲基咪唑后继续搅拌均匀制备成胶液。
用此胶液浸渍2116玻璃纤维布(基重105g/m 2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为55％的预浸料。将4片预浸料重叠，在该层叠体上下两面各覆盖一张厚度为12μm的电解铜箔，置于可程式控温控压的真空压机中，在真空状态，在25kgf/cm 2的压力条件，制品温度在200℃条件下固化100分钟，制成0.4mm厚度的覆铜箔层压板。
实施例6：
依次将5份的改性炭黑3、70份双酚A环氧树脂、30份的酚醛型固化剂溶于按质量比1:1:1配比的丁酮、甲苯、丙二醇甲醚混合溶剂中后，于搅拌条件下加入25份的氧化铝、35份的二氧化硅、2份的硅烷偶联剂和2份的2-甲基咪唑后继续搅拌均匀制备成胶液。
用此胶液浸渍2116玻璃纤维布(基重105g/m 2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为55％的预浸料。将4片预浸料重叠，在该层叠体上下两面各覆盖一张厚度为12μm的电解铜箔，置于可程式控温控压的真空压机中，在真空状态，在25kgf/cm 2的压力条件，制品温度在200℃条件下固化100分钟，制成0.4mm厚度的覆铜箔层压板。
对比例1：
依次将5份的未改性炭黑、70份双酚A环氧树脂、30份的酚醛型固化剂溶于按质量比1:1:1配比的丁酮、甲苯、丙二醇甲醚混合溶剂中后，于搅拌条件下加入25份的氧化铝、35份的二氧化硅、2份的硅烷偶联剂和2份的2-甲基咪唑 后继续搅拌均匀制备成胶液。
用此胶液浸渍2116玻璃纤维布(基重105g/m 2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为55％的预浸料。将4片预浸料重叠，在该层叠体上下两面各覆盖一张厚度为12μm的电解铜箔，置于可程式控温控压的真空压机中，在真空状态，在25kgf/cm 2的压力条件，制品温度在200℃条件下固化100分钟，制成0.4mm厚度的覆铜箔层压板。
对比例2：
依次将5份的对比改性炭黑(其原料和制备方法同实施例1，区别在于以聚丙烯酸作为改性高分子)、70份双酚A环氧树脂、30份的酚醛型固化剂溶于质量比按1:1:1配比的丁酮、甲苯、丙二醇甲醚混合溶剂中后，于搅拌条件下加入25份的氧化铝、35份的二氧化硅、2份的硅烷偶联剂和2份的2-甲基咪唑后继续搅拌均匀制备成胶液。
用此胶液浸渍2116玻璃纤维布(基重105g/m 2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为55％的预浸料。将4片预浸料重叠，在该层叠体上下两面各覆盖一张厚度为12μm的电解铜箔，置于可程式控温控压的真空压机中，在真空状态，在25kgf/cm 2的压力条件，制品温度在200℃条件下固化100分钟，制成0.4mm厚度的覆铜箔层压板。
对实施例1-6和对比例1-2制作得到的覆铜箔层压板进行性能测试：
(1)测试方法：
色泽：目测；
玻璃化转变温度(TG)：依据IPC-TM650 2.4.25测试；
透光率：使用透光率测试仪测试；
体积电阻和表面电阻：依据IPC-TM650 2.5.17.1测试；
分散性：改性炭黑和未改性炭黑的水溶液在离心机中离心60min前后分别测试透光率，离心前后透光率差值越大代表分散越不均匀，即分散性越差。
(2)测试结果如下表1所示：
表1
Figure PCTCN2020088414-appb-000003
注：水溶液分散性差值数值越大代表分散性越差。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (14)

  1. 一种改性炭黑，其特征在于，包括炭黑以及改性基团；
    所述炭黑的表面具有酰氯基团；所述改性基团由改性高分子与所述酰氯基团反应接枝而成；所述改性高分子为醇类高分子。
  2. 根据权利要求1所述的改性炭黑，其特征在于，所述炭黑的粒径为5～100nm。
  3. 根据权利要求2所述的改性炭黑，其特征在于，所述炭黑的粒径为5～50nm。
  4. 一种改性炭黑的制备方法，其特征在于，包括如下步骤：
    (1)通过液相法对炭黑进行表面氧化改性，然后酰氯化，以在所述炭黑的表面形成酰氯基团；
    (2)混合所述表面形成有酰氯基团的炭黑和改性高分子，进行接枝反应以形成改性基团；所述改性高分子选自醇类高分子。
  5. 根据权利要求4所述的改性炭黑的制备方法，其特征在于，所述炭黑的粒径为5～100nm。
  6. 根据权利要求5所述的改性炭黑的制备方法，其特征在于，所述炭黑的粒径为5～50nm。
  7. 根据权利要求4-6任一项所述的改性炭黑的制备方法，其特征在于，步骤(1)中，所述表面氧化改性包括如下步骤：
    将氧化剂和所述炭黑混合，在20～30℃下反应；然后用水对反应所得固体进行清洗，干燥。
  8. 根据权利要求7所述的改性炭黑的制备方法，其特征在于，所述氧化剂为硝酸、过氧化氢和过硫酸铵中的任意一种。
  9. 根据权利要求8所述的改性炭黑的制备方法，其特征在于，
    当所述氧化剂为硝酸时，所述反应的时间为1.5～2.5h；
    当所述氧化剂为过氧化氢时，所述反应的时间为95～97h；
    当所述氧化剂为过硫酸铵时，所述反应的时间为23～25h。
  10. 根据权利要求4-6任一项所述的改性炭黑的制备方法，其特征在于，步骤(1)中，所述酰氯化的方法为：于溶剂中，将所述表面氧化改性后的炭黑与二氯亚砜混合，于35～45℃反应8～12h。
  11. 根据权利要求4-6任一项所述的改性炭黑的制备方法，其特征在于，步骤(2)中，所述接枝反应包括如下步骤：
    于溶剂中，混合所述表面形成有酰氯基团的炭黑和改性高分子，于50～90℃反应10～30h。
  12. 一种树脂组合物，其特征在于，包括权利要求1-3任一项所述的改性炭 黑或权利要求4-11任一项所述的制备方法制备得到的改性炭黑。
  13. 根据权利要求12所述的树脂组合物，其特征在于，以重量百分比计，由包括如下组分的原料制备而成：
    Figure PCTCN2020088414-appb-100001
  14. 一种覆铜板，其特征在于，其采用的胶料为权利要求12或13所述树脂组合物。
PCT/CN2020/088414 2019-12-04 2020-04-30 改性炭黑及其制备方法、树脂组合物、覆铜板 WO2021109442A1 (zh)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US17/627,083 US20220267608A1 (en) 2019-12-04 2020-04-30 Modified carbon black and production method therefor, resin composition, and copper clad laminate
JP2022502505A JP7457787B2 (ja) 2019-12-04 2020-04-30 変性カーボンブラック及びその製造方法、樹脂組成物、銅張積層板
KR1020227018460A KR20220092582A (ko) 2019-12-04 2020-04-30 변성 카본블랙, 이의 제조방법, 수지 조성물 및 동박적층판

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201911226294.9A CN111057270B (zh) 2019-12-04 2019-12-04 改性炭黑及其制备方法、树脂组合物、覆铜板
CN201911226294.9 2019-12-04

Publications (1)

Publication Number Publication Date
WO2021109442A1 true WO2021109442A1 (zh) 2021-06-10

Family

ID=70299676

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/088414 WO2021109442A1 (zh) 2019-12-04 2020-04-30 改性炭黑及其制备方法、树脂组合物、覆铜板

Country Status (6)

Country Link
US (1) US20220267608A1 (zh)
JP (1) JP7457787B2 (zh)
KR (1) KR20220092582A (zh)
CN (1) CN111057270B (zh)
TW (1) TWI818179B (zh)
WO (1) WO2021109442A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111057270B (zh) * 2019-12-04 2021-08-31 广东盈骅新材料科技有限公司 改性炭黑及其制备方法、树脂组合物、覆铜板

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1408778A (zh) * 2002-09-24 2003-04-09 天津大学 具有优良水分散性接枝炭黑的制造方法
US20100283174A1 (en) * 2009-05-08 2010-11-11 Yuan Ze University Fabrication of polymer grafted carbon nanotubes/polypropylene composite bipolar plates for fuel cell
CN105461988A (zh) * 2015-12-30 2016-04-06 付文 一种绿色轮胎用改性炭黑/tpi/橡胶复合材料的制备方法
CN111057270A (zh) * 2019-12-04 2020-04-24 广东盈骅新材料科技有限公司 改性炭黑及其制备方法、树脂组合物、覆铜板

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3632558B2 (ja) 1999-09-17 2005-03-23 日立化成工業株式会社 封止用エポキシ樹脂組成物及び電子部品装置
US6402825B1 (en) 2001-07-27 2002-06-11 Lexmark International, Inc Surface modified carbon black
KR100644681B1 (ko) 2005-01-31 2006-11-10 삼성전자주식회사 표면 개질된 착색제를 포함한 잉크 조성물
JP2008111071A (ja) * 2006-10-31 2008-05-15 Yokohama Rubber Co Ltd:The ゴム組成物及びそれを用いたランフラット性能を有する空気入りタイヤ
CN101855302B (zh) 2007-08-23 2014-10-01 森馨颜色公司 自分散颜料及制造和使用该自分散颜料的方法
TWI605096B (zh) * 2012-02-29 2017-11-11 大同化成工業股份有限公司 黑色矩陣用碳黑及其製造方法
CN104527177B (zh) * 2014-12-16 2018-03-23 艾达索高新材料芜湖有限公司 一种用于印刷电路板的可回收半固化片、固化片、覆铜板及其制备、回收方法
JP6592263B2 (ja) 2015-03-26 2019-10-16 東海カーボン株式会社 酸化カーボンブラック粒子水分散体の製造方法
CN104788685B (zh) * 2015-04-28 2017-08-25 中科院广州化学有限公司南雄材料生产基地 一种改性炭黑及其制备方法与应用
KR102287542B1 (ko) * 2016-08-08 2021-08-11 도레이 카부시키가이샤 수지 조성물, 그것을 사용한 시트, 적층체, 파워 반도체 장치, 플라스마 처리 장치 및 반도체의 제조 방법
CN106634059B (zh) * 2016-12-16 2018-05-25 江南大学 一种水性自分散纳米炭黑的制备方法
JP7210901B2 (ja) 2017-06-26 2023-01-24 味の素株式会社 樹脂組成物層
CN108749240B (zh) * 2018-06-22 2020-05-05 重庆云天化瀚恩新材料开发有限公司 一种绝缘层不透光的挠性覆铜板、其制备方法及其应用
CN110305445A (zh) * 2019-05-16 2019-10-08 浙江华正新材料股份有限公司 一种黑色树脂组合物、预浸料和层压板

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1408778A (zh) * 2002-09-24 2003-04-09 天津大学 具有优良水分散性接枝炭黑的制造方法
US20100283174A1 (en) * 2009-05-08 2010-11-11 Yuan Ze University Fabrication of polymer grafted carbon nanotubes/polypropylene composite bipolar plates for fuel cell
CN105461988A (zh) * 2015-12-30 2016-04-06 付文 一种绿色轮胎用改性炭黑/tpi/橡胶复合材料的制备方法
CN111057270A (zh) * 2019-12-04 2020-04-24 广东盈骅新材料科技有限公司 改性炭黑及其制备方法、树脂组合物、覆铜板

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WEN FU ET AL.: "Research of In Situ Grafted Carbon Black", APPLIED MECHANICS AND MATERIALS, vol. 464, 30 November 2013 (2013-11-30), pages 41 - 43, XP055818037 *

Also Published As

Publication number Publication date
JP2022541470A (ja) 2022-09-26
JP7457787B2 (ja) 2024-03-28
CN111057270A (zh) 2020-04-24
CN111057270B (zh) 2021-08-31
KR20220092582A (ko) 2022-07-01
US20220267608A1 (en) 2022-08-25
TWI818179B (zh) 2023-10-11
TW202122502A (zh) 2021-06-16

Similar Documents

Publication Publication Date Title
CN102786704B (zh) 一种黑色聚酰亚胺薄膜的制备方法
JP2017125196A (ja) 合成樹脂並びにそれらから製造されるワニス、プレプレグおよび積層物
CN103225210B (zh) 一种表面接枝改性的芳纶纤维及其制备方法
WO2021103850A1 (zh) 一种改性碳纳米管的制备方法及其应用
CN110330782B (zh) 一种改性氧化石墨烯/聚氨酯耐热复合材料的制备方法
Liu et al. Significantly improved interfacial properties and wave-transparent performance of PBO fibers/cyanate esters laminated composites via introducing a polydopamine/ZIF-8 hybrid membrane
WO2017201987A1 (zh) 一种抗静电复合纳米材料薄膜及其制备方法
WO2021128691A1 (zh) 环氧改性硅树脂组合物及其应用
WO2021109442A1 (zh) 改性炭黑及其制备方法、树脂组合物、覆铜板
WO2014036712A1 (zh) 复合材料、用其制作的高频电路基板及其制作方法
CN108410016A (zh) 一种改性钛酸钡纳米颗粒及其制备方法和一种改性聚合物复合薄膜及其制备方法
CN107434945A (zh) 氟系树脂的非水系分散体、使用其的含氟系树脂的热固化树脂组合物和其固化物
Peng et al. Fabrication of low dielectric constant fluorinated poly (arylene ether nitrile) composites by cross-linking with metal-organic frameworks
JP2008291154A (ja) 熱硬化性樹脂組成物、コアシェルポリマ、硬化物
CN115895378B (zh) 一种氟素离型涂料及其制备方法
WO2024011919A1 (zh) 一种eva材料的制备方法及eva材料
WO2020248501A1 (zh) 活性酯化合物、树脂组合物及具有其的半固化片、绝缘薄膜、覆金属箔层压板、印制线路板
JP6755643B2 (ja) アリルエーテル変性ビフェニルアラルキルノボラック樹脂、アリル変性ビフェニルアラルキルノボラック樹脂、その製造方法、及びそれを用いた組成物
JPWO2020027189A1 (ja) 金属張積層板、プリント配線板およびその製造方法
CN109180936A (zh) 一种本征黑色聚酰亚胺薄膜及其制备方法与用途
WO2019127389A1 (zh) 环氧树脂组合物、预浸料、层压板和印刷电路板
JP2010001346A (ja) 熱硬化性樹脂組成物及び硬化物
JP2012136713A (ja) コアシェルポリマ
JP2012214776A (ja) 透明基板用エポキシ組成物、プリプレグ、及び透明基板
Wang et al. High‐yield water‐phase exfoliated few‐defect graphene for high performance polymer nanocomposites

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: 20896118

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022502505

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20227018460

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20896118

Country of ref document: EP

Kind code of ref document: A1