CN111154330A - Heat-conducting insulating ink, preparation method and application thereof to copper foil adhesive tape - Google Patents

Heat-conducting insulating ink, preparation method and application thereof to copper foil adhesive tape Download PDF

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Publication number
CN111154330A
CN111154330A CN202010126549.0A CN202010126549A CN111154330A CN 111154330 A CN111154330 A CN 111154330A CN 202010126549 A CN202010126549 A CN 202010126549A CN 111154330 A CN111154330 A CN 111154330A
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heat
parts
resin
modified
conducting
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CN111154330B (en
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顾正青
王开吉
陈启峰
周奎任
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Suzhou Shihua New Material Technology Co ltd
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Suzhou Shihua New Material Technology Co ltd
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    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C09D11/104—Polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B41M1/10—Intaglio printing ; Gravure printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B41M1/26—Printing on other surfaces than ordinary paper
    • B41M1/28—Printing on other surfaces than ordinary paper on metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C09D11/104—Polyesters
    • C09D11/105—Alkyd resins
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/108—Hydrocarbon resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/28—Metal sheet

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The invention discloses heat-conducting insulating ink which comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by mass: 30-40 parts of modified crystal resin, 5-10 parts of non-crystalline resin, 8-10 parts of pigment, 10-15 parts of modified heat-conducting filler, 1-2 parts of auxiliary agent and 70-80 parts of solvent; the component B is an isocyanate curing agent, and the using amount of the component B is 4-10% of that of the component A. Meanwhile, the invention also discloses a preparation method of the heat-conducting insulating ink and application of the heat-conducting insulating ink to a copper foil adhesive tape. The heat-conducting insulating ink obtained by the invention is applied to a copper foil tape, the heat-conducting coefficient of the obtained heat-conducting printing layer is more than or equal to 4W/(M.K), the roughness is less than or equal to 3 mu M, and the volume resistivity is 1013~16Omega cm, the adhesive force level of the copper foil surface printing layer is 5B, the surface energy is more than or equal to 46mN/m, and the appearance and performance requirements of the copper foil adhesive tape in the 3C product are met.

Description

Heat-conducting insulating ink, preparation method and application thereof to copper foil adhesive tape
Technical Field
The invention relates to the field of printing ink, in particular to heat-conducting insulating printing ink, a preparation method and application thereof in a copper foil tape.
Background
Electromagnetic shielding adhesive tapes are commonly used in electronic products such as mobile phones and computers, and are used for reducing the influence of electromagnetic signals on components of the electronic products and reducing the influence of radiation generated by the electronic products on the health of human bodies. The electronic equipment can generate a large amount of heat in high-frequency electromagnetic signal transmission and needs to be removed in time, otherwise, the service life of the electronic equipment and the operation efficiency of the electronic equipment are reduced.
In the design and application process of the product, the copper foil adhesive tape at a special position is required to be endowed with specific functions such as heat conductivity, electric conductivity or insulativity and the like on the premise of meeting the shielding performance, for example, the positions at two sides of the luminescent screen of an electronic product are bonded with the black copper foil adhesive tape, so that the risk of light leakage at two sides of the luminescent screen caused by the improvement of the high brightness and low thickness requirements of the screen can be reduced, and the electromagnetic shielding requirement is met. The excellent conductivity of copper foil itself can impart conductivity to the tape, but it is still a hot spot of research on copper foil tapes with insulation requirements.
The copper foil tape can improve the insulativity by bonding a PET tape on the non-adhesive surface, but the PET tape is easy to shrink by heating to cause edge shrinkage abnormality, so the PET tape is replaced by a non-adhesive surface ink printing mode. The main components of the ink are synthetic resin, pigment and filler, solvent and other additives, the thermal conductivity of various components of the ink after layer-by-layer drying is poor, the copper foil tape cannot be endowed with good heat conduction and radiation performance, and the thermal conductivity of a printing layer is improved by adding the thermal conductive filler.
Patent CN204733501U discloses a heat sink with electromagnetic interference shielding function, which refers to a heat conductive ink printed on a metal layer, wherein the heat conductive ink adopts metal powder and inorganic heat conductive powder with good heat conductivity to be added into an ink layer, which can obviously improve the heat conductivity of the ink, but the addition of the metal powder enhances the electrical conductivity of the ink.
Patent CN102711421A discloses a shielding and heat dissipating material, which uses a copper foil with high thermal conductivity as a functional layer, and adds a thermal conductive filler into a resin to prepare an ink, and the ink is coated on the surface of the functional layer to obtain a material with good shielding and heat dissipating effects. However, the ink synthesized by the patent cannot meet the requirement on insulation, and meanwhile, the compatibility between the resin and the heat-conducting filler is not improved, so that the storage time is short, the defect of pigment sedimentation is easy to occur when the viscosity is small, and the application range of the ink is severely limited.
The patent CN110343419A discloses a high-thermal-conductivity insulating polyimide ink and a preparation method thereof, epoxy modification is carried out on thermal-conductivity filler graphene and carbon nanotubes, then the thermal-conductivity filler graphene and carbon nanotubes are added into polyimide resin, and a solvent and an auxiliary agent are added to synthesize the ink, wherein the modification of the thermal-conductivity filler improves the insulativity of an ink printing layer, and simultaneously forms a thermal-conductivity network and improves the thermal conductivity of the printing layer; however, the resin content as the main component is high, so that the overall heat conducting performance of the printing layer is limited, and after the heat conducting fillers graphene and carbon nano tubes are epoxidized, the damage of the electric conducting structure of the heat conducting fillers causes the change of the heat conducting structure, so that the heat conductivity is obviously reduced.
Therefore, the development of a heat-conducting ink which has stable use performance, good insulation and heat conductivity after the ink layer is dried and does not fall off in an adhesion test on a copper foil is urgently needed.
Disclosure of Invention
The invention aims to solve the technical problems and provides heat-conducting insulating ink, a preparation method and application thereof in a copper foil tape.
The heat-conducting insulating oil obtained by the inventionThe ink is applied to the copper foil adhesive tape, the heat conductivity coefficient of the obtained heat-conducting printing layer is more than or equal to 4W/(M.K), the roughness is less than or equal to 3 mu M, and the volume resistivity is 1013~16Omega cm, the adhesive force level of the copper foil surface printing layer is 5B, the surface energy is more than or equal to 46mN/m, the appearance and performance requirements of the copper foil adhesive tape in the 3C product are met, and the scheme is as follows.
A heat-conducting insulating ink comprises a component A and a component B. The component A comprises the following raw materials in parts by weight: 30-40 parts of modified crystal resin, 5-10 parts of non-crystalline resin, 8-10 parts of pigment, 10-15 parts of modified heat-conducting filler, 1-2 parts of auxiliary agent and 70-80 parts of solvent; the component B is an isocyanate curing agent, and the using amount of the component B accounts for 4-10% of the mass ratio of the component A.
As a preferable scheme of the scheme, the modified crystal form resin is at least one of modified crystal form polyester resin and modified crystal form polypropylene resin, the number average molecular weight is 80000-300000, the softening point is 100-150 ℃, and the acid value is 2-30 mgKOH/g; the modified crystal-form resin can form a heat conduction channel with the filler after being crystallized, and the heat conduction coefficient of the printing layer can be greatly improved; the modified crystal polyester resin is preferred, the number average molecular weight is 100000-150000, the modified crystal polyester resin is high in crystallinity, the modification steps are simple, and the modification degree is easy to control.
As a preferable scheme of the scheme, the amorphous resin is at least one of amorphous polyester resin, amorphous epoxy resin, amorphous polyurethane resin, amorphous polyamide resin, amorphous acrylic resin and amorphous alkyd resin, the number average molecular weight is 20000-40000, the softening point is 20-90 ℃, and the hydroxyl value is 3-10 mgKOH/g; the amorphous resin and the crystalline resin are compounded for use, so that the adhesive force of the printing ink layer to the copper foil can be improved, the brittleness of the printing ink layer can be reduced, and the surface energy of the printing layer can be improved.
As a preferable scheme of the scheme, the modified heat-conducting filler is at least one of boron nitride, aluminum nitride, silicon nitride and silicon carbide modified by ultrasonic waves or coupling agents; the adoption of the insulating heat-conducting filler can avoid the formation of a conductive path after the ink layer is dried, and endows the ink layer with heat conductivity.
As a preferable scheme of the scheme, the modified crystal polyester resin is obtained by performing polycondensation on at least one of polyhydric alcohols neopentyl glycol, 1, 6-hexanediol, trimethylolpropane, diethylene glycol, 1, 4-cyclohexanediol and 1, 4-butanediol and at least one of polybasic acids adipic acid, 1, 12-dodecanedioic acid, succinic acid, itaconic acid, 1, 4-cyclohexanedicarboxylic acid and terephthalic acid to obtain a prepolymer, and then modifying the prepolymer with maleic anhydride; the modification of the maleic anhydride improves the crystallinity of the crystal polyester resin, improves the solubility of the crystal polyester resin in an organic solvent, improves the compatibility with the modified heat-conducting filler, can excellently wrap the modified heat-conducting filler, can form a heat-conducting network after crystallization, and improves the heat conductivity of the ink printing layer.
As a preferred scheme of the scheme, the modified crystal form polypropylene resin is obtained by blending and melting polypropylene resin and β -nucleating agent to obtain a prepolymer and then modifying the prepolymer by maleic anhydride, wherein polar groups are introduced into a nonpolar polypropylene structure by maleic anhydride, so that the high crystallinity and high strength of polypropylene are kept, the compatibility of the modified heat-conducting filler and the polypropylene is greatly improved, the solubility of the crystal form polypropylene resin in an organic solvent is improved, the adhesion of the resin to a base material is improved by introducing the polar groups, and the defect of poor adhesion of the crystal form polypropylene resin to the base material is overcome.
As a preferred scheme of the scheme, the ultrasonic modified heat-conducting filler is obtained by adding the heat-conducting filler after annealing treatment into at least one of alcohol solvents, namely absolute ethyl alcohol, isopropanol and n-butanol, and then carrying out ultrasonic treatment; the coupling agent modified heat-conducting filler is surface modified by adding at least one of silane coupling agent, titanate coupling agent and aluminate coupling agent; the surface of the heat-conducting filler is hydroxylated by annealing treatment, and the heat-conducting filler can be stably existed after the particle size of the heat-conducting filler is refined by ultrasonic treatment and coupling agent modification.
The modified crystal-form resin introduces polar groups due to modification of maleic anhydride, and has strong binding force with hydroxyl groups on the surface of the modified pigment, so that the modified pigment can be uniformly dispersed in the modified crystal-form resin, and the ink is stable and is not easy to settle in the using and storing processes; meanwhile, the amorphous resin and the crystalline resin are compounded, so that the brittleness of the ink layer is reduced, and the adhesive force of the ink layer is enhanced.
In a preferred embodiment of the present invention, the pigment is at least one of insulating carbon black and barium sulfate. The insulating carbon black and the barium sulfate have good insulativity, are black and white common pigments respectively, and cannot have great adverse effect on the insulativity of the ink layer when being added into the ink for use.
The invention also discloses a preparation method of the heat-conducting and insulating ink, which comprises the following steps: 1) adding the modified crystalline resin, the amorphous resin and the solvent into a container, and mechanically stirring for 2-3 hours until the resin is completely dissolved, preferably mechanically stirring for 3 hours; 2) adding the modified heat-conducting filler, the pigment and the auxiliary agent into the resin solution and stirring for 1-2 h; 3) sanding for 2-4 h by using a sand mill until the particle size fineness is less than 3 mu m; 4) filtering with 400 mesh filter cloth to obtain component A; 5) and (3) adding the component B into the component A in the step 4) to obtain the heat-conducting and insulating ink.
As a preferable scheme of the scheme, the preparation method of the modified crystal form polyester resin comprises the following steps: 1) adding polyalcohol and polybasic acid into a reaction container, mixing for 1-1.5 h at 60-80 ℃, gradually heating to 180-240 ℃ for reaction for 2-6 h until the water yield is not lower than 95% of a theoretical value, and cooling to 150 ℃; 2) adding maleic anhydride, and reacting for 3-5 h under the condition of heat preservation until the acid value is 2-30 mgKOH/g; 3) cooling to room temperature, and washing with absolute ethyl alcohol for 2-4 times; 4) drying for 2-3 h at 60 ℃.
As a preferable scheme of the scheme, the modified crystal form polypropylene resin comprises the following steps of 1) adding polypropylene and β -nucleating agent into a container, heating to 150-200 ℃ for high-temperature melting for 3-5 h until the molecular weight is 80000-200000, cooling to 150 ℃, 2) adding maleic anhydride for heat preservation reaction for 3-5 h until the acid value is 2-30 mgKOH/g, 3) cooling to room temperature, washing with absolute ethyl alcohol for 2-4 times, and 4) drying at 60 ℃ for 2-3 h.
As a preferable scheme of the scheme, the ultrasonic modified heat-conducting filler comprises the following steps: 1) heating a proper amount of heat-conducting filler to 1000 ℃ and preserving heat for 2-3 hours; 2) naturally cooling to room temperature, and then putting the mixture into an alcohol solvent for ultrasonic treatment for 5-8 hours to form heat-conducting filler slurry; 3) and (3) carrying out suction filtration on the heat-conducting filler slurry obtained in the step 2), repeatedly washing the heat-conducting filler slurry with absolute ethyl alcohol, and drying the heat-conducting filler slurry in an oven at the temperature of 60-80 ℃ for 2-3 hours to obtain the modified heat-conducting filler.
As a preferable scheme of the scheme, the coupling agent modified heat-conducting filler comprises the following steps: 1) heating a proper amount of heat-conducting filler to 1000 ℃ and preserving heat for 2-3 hours; 2) naturally cooling to room temperature, adding the heat-conducting filler and the coupling agent into the alcohol solvent, and mechanically stirring for 3-6 hours to form a mixed solution; 3) ball-milling the mixed solution in the step 2) for 2-4 h by using a ball mill; 4) and (3) carrying out suction filtration on the mixed solution in the step 3), repeatedly washing the mixed solution with absolute ethyl alcohol, and drying the washed mixed solution in an oven at the temperature of 60-80 ℃ for 2-3 hours to obtain the modified heat-conducting filler.
The invention also discloses an application of the heat-conducting insulating ink in a copper foil adhesive tape, which comprises the following raw materials in parts by mass: 50-60 parts of a heat-conducting and insulating ink component A, 60-70 parts of an organic solvent, and 4-10% of a component B isocyanate curing agent in the proportion of the component A.
Compared with the prior art, the heat-conducting insulating ink obtained by the invention and the application thereof on the copper foil adhesive tape have the following advantages.
(1) The crystal form resin is modified by maleic anhydride and then is soluble in an organic solvent, and meanwhile, the crystallinity of the crystal form resin after drying is improved, and the thermal conductivity of the printing ink main body resin is improved.
(2) The modified crystal-form resin and the modified heat-conducting filler both contain more polar bonds, the modified heat-conducting filler can be uniformly dispersed into the modified crystal-form resin, the modified crystal-form resin is crystallized in the drying process to form a heat-conducting network, and the heat-conducting coefficient is more than or equal to 4W/(M.K).
(3) The complex use of the modified crystal-form resin and the amorphous resin can improve the thermal conductivity of the printing layer, improve the flexibility of the printing layer, reduce the brittleness of the printing layer, improve the adhesive force of the printing ink to the copper foil, and simultaneously ensure that the surface energy of the printing layer is more than or equal to 46 mN/m.
(4) The heat-conducting filler and the pigment with higher insulativity are adopted, so that the insulativity of the ink layer can be improved.
(5) The ink prepared by the method has the advantages of fineness less than 3 mu m, good storage stability, no sedimentation in the process of dilution and use, low viscosity, suitability for gravure and micro-gravure printing, uniform and fine printing layer and roughness less than or equal to 3 mu m.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.
The dispersed thermal conductive and insulating inks obtained in the following examples were tested after application according to the following procedure: and (3) coating the heat-conducting insulating ink on a copper foil by using a RK coating machine and a matched 2# wire rod, drying for 2min at 120 ℃, and testing the performance after curing for 24h at 48 ℃.
Comparative example 1.
1) 40 parts of GK810 resin (Tokusan, Japan) are added to 70 parts of toluene and mechanically stirred for 3 hours until complete dissolution.
2) 9 parts of MA-7 carbon black (Mitsubishi), 15 parts of boron nitride BN-10 (Shanghai hundred Charantia) and 1 part of wetting dispersant D-2013(BYK) are added into the resin solution and mechanically stirred for 1 hour.
3) And (3) taking the mixture obtained in the step 2), putting the mixture into a sand mill, sanding for 3 hours, and filtering with 400-mesh filter cloth to obtain the component A of the ink.
4) And (3) adding 60 parts of butanone serving as a solvent and 3 parts of isocyanate curing agent N-3390 (Bayer) serving as the component A of the ink in the step 3), and mechanically stirring for 30min to obtain the well-dispersed heat-conducting insulating ink.
The basic properties of the thermally conductive and insulating ink and the thermally conductive and insulating ink printed layer are detailed in table 1.
Comparative example 2.
1) Mixing 40 parts of neopentyl glycol and 30 parts of terephthalic acid at 80 ℃ for 1.5h in a reaction vessel, gradually heating to 220 ℃ for reaction for 6h until the water yield is not lower than 95% of the theoretical value, and cooling to 150 ℃; adding 15 parts of maleic anhydride, and reacting for 5 hours under the condition of heat preservation until the acid value is 2-30 mgKOH/g; cooling to room temperature, and washing with anhydrous ethanol for 3 times; drying for 3h at 60 ℃ to obtain the modified crystal resin.
2) 9 parts of MA-7 carbon black (Mitsubishi), 15 parts of boron nitride BN-10 (Shanghai hundred Charantia) and 1 part of wetting dispersant D-2013(BYK) are added into the resin solution and mechanically stirred for 1 hour.
3) And (3) taking the mixture obtained in the step 2), putting the mixture into a sand mill, sanding for 3 hours, and filtering with 400-mesh filter cloth to obtain the component A of the ink.
4) And (3) adding 60 parts of butanone serving as a solvent and 3 parts of isocyanate curing agent N-3390 (Bayer) serving as the component A of the ink in the step 3), and mechanically stirring for 30min to obtain the well-dispersed heat-conducting insulating ink.
The basic properties of the thermally conductive and insulating ink and the thermally conductive and insulating ink printed layer are detailed in table 1.
Example 1.
1) Mixing 25 parts of 1, 6-hexanediol and 15 parts of 1, 12-dodecanedioic acid in a reaction container at 80 ℃ for 1.5h, gradually heating to 220 ℃ for reaction for 6h until the water yield is not lower than 95% of a theoretical value, and cooling to 150 ℃; adding 10 parts of maleic anhydride, and reacting for 5 hours under the condition of heat preservation until the acid value is 2-30 mgKOH/g; cooling to room temperature, and washing with anhydrous ethanol for 3 times; drying for 3h at 60 ℃ to obtain the modified crystal polyester resin.
2) Taking 15 parts of boron nitride BN-10 (Shanghai hundred figures), heating to 1000 ℃, and preserving heat for 3 hours; naturally cooling to room temperature, and then putting the mixture into isopropanol to perform ultrasonic treatment for 5 hours to form heat-conducting filler slurry; and (3) carrying out suction filtration on the heat-conducting filler slurry, repeatedly washing the heat-conducting filler slurry by using absolute ethyl alcohol, and drying the heat-conducting filler slurry in an oven at the temperature of 80 ℃ for 3 hours to obtain the modified boron nitride.
3) Adding 40 parts of the modified crystal polyester resin obtained in the step 1) and 5 parts of GK888 (Nippon Tokusho) into 40 parts of toluene and 30 parts of butanone solution, and mechanically stirring for 3 hours until the modified crystal polyester resin and the GK888 are completely dissolved.
4) And (3) adding 9 parts of MA-7 carbon black (Mitsubishi), 15 parts of modified boron nitride in the step 2) and 1 part of wetting dispersant D-2013(BYK) into the resin solution in the step 3), and mechanically stirring for 1 hour.
5) And (3) taking the mixture obtained in the step 4), putting the mixture into a sand mill, sanding for 3 hours, and filtering with 400-mesh filter cloth to obtain the component A of the ink.
6) And (3) taking 50 parts of the ink A component in the step 5), adding 60 parts of butanone serving as a solvent and 3 parts of isocyanate curing agent N-3390 (Bayer) serving as the ink B component, and mechanically stirring for 30min to obtain the well-dispersed heat-conducting insulating ink.
The basic properties of the thermally conductive and insulating ink and the thermally conductive and insulating ink printed layer are detailed in table 1.
Example 2.
1) Adding 25 parts of polypropylene J-580S (Korea SK) and 0.12 part of β -nucleating agent N, N-dicyclohexyl phthalic acid amide into a container, heating to 200 ℃ for high-temperature melting for 5 hours until the molecular weight is 150000, cooling to 150 ℃, adding 15 parts of maleic anhydride for heat preservation reaction for 5 hours until the acid value is 2-30 mgKOH/g, cooling to room temperature, washing with absolute ethyl alcohol for 4 times, and drying at 60 ℃ for 3 hours to obtain the modified crystal form polypropylene resin.
2) Taking 15 parts of nano silicon carbide (Beijing Jia Anheng), heating to 1000 ℃, and preserving heat for 3 hours; after cooling to room temperature, adding the nano silicon carbide and 0.15 part of silane coupling agent KH-550 into an alcohol solvent, and mechanically stirring for 6 hours to form a mixed solution; ball milling is carried out for 4h by using a ball mill, after suction filtration, absolute ethyl alcohol is used for repeatedly washing, and the mixture is put into a 60 ℃ oven for drying for 3h to obtain the modified silicon carbide.
3) Adding 40 parts of the modified crystal form polypropylene resin obtained in the step 1) and 5 parts of GK888 (Nippon Toyobo) into 40 parts of toluene and 30 parts of butanone solution, and mechanically stirring for 3 hours until the modified crystal form polypropylene resin and the GK888 are completely dissolved.
4) And (3) adding 9 parts of MA-7 carbon black (Mitsubishi), 15 parts of modified silicon carbide in the step 2) and 1 part of wetting dispersant D-2013(BYK) into the resin solution in the step 3), and mechanically stirring for 1 hour.
5) Taking the mixture obtained in the step 4), placing the mixture into a sand mill, sanding for 3 hours, and filtering with 400-mesh filter cloth to obtain a component A of the printing ink;
6) and (3) taking 50 parts of the ink A component in the step 5), adding 60 parts of butanone serving as a solvent and 3 parts of isocyanate curing agent N-3390 (Bayer) serving as the ink B component, and mechanically stirring for 30min to obtain the well-dispersed heat-conducting insulating ink.
The basic properties of the thermally conductive and insulating ink and the thermally conductive and insulating ink printed layer are detailed in table 1.
Example 3.
1) Mixing 25 parts of 1, 4-butanediol and 15 parts of terephthalic acid at 80 ℃ for 1.5h in a reaction vessel, gradually heating to 220 ℃ for reaction for 6h until the water yield is not lower than 95% of the theoretical value, and cooling to 150 ℃; adding 10 parts of maleic anhydride, and reacting for 5 hours under the condition of heat preservation until the acid value is 2-30 mgKOH/g; cooling to room temperature, and washing with anhydrous ethanol for 3 times; drying for 3h at 60 ℃ to obtain the modified crystal polyester resin.
2) Taking 15 parts of nano silicon carbide (Beijing Jia Anheng), heating to 1000 ℃, and preserving heat for 3 hours; after cooling to room temperature, adding the nano silicon carbide and 0.15 part of silane coupling agent KH-550 into an alcohol solvent, and mechanically stirring for 6 hours to form a mixed solution; ball milling is carried out for 4h by using a ball mill, after suction filtration, absolute ethyl alcohol is used for repeatedly washing, and the mixture is put into a 60 ℃ oven for drying for 3h to obtain the modified silicon carbide.
3) Adding 40 parts of the modified crystal polyester resin obtained in the step 1) and 5 parts of GK888 (Nippon Tokusho) into 40 parts of toluene and 30 parts of butanone solution, and mechanically stirring for 3 hours until the modified crystal polyester resin and the GK888 are completely dissolved.
4) And (3) adding 9 parts of barium sulfate BF-20 (chemical in Japan), 15 parts of modified silicon carbide in the step 2) and 1 part of wetting dispersant D-2013(BYK) into the resin solution in the step 3), and mechanically stirring for 1 hour.
5) And (3) taking the mixture obtained in the step 4), putting the mixture into a sand mill, sanding for 3 hours, and filtering with 400-mesh filter cloth to obtain the component A of the ink.
6) And (3) taking 50 parts of the ink A component in the step 5), adding 60 parts of butanone serving as a solvent and 3 parts of isocyanate curing agent N-3390 (Bayer) serving as the ink B component, and mechanically stirring for 30min to obtain the well-dispersed heat-conducting insulating ink.
The basic properties of the thermally conductive and insulating ink and the thermally conductive and insulating ink printed layer are detailed in table 1.
Example 4.
1) Mixing 25 parts of neopentyl glycol and 15 parts of terephthalic acid at 80 ℃ for 1.5h in a reaction vessel, gradually heating to 220 ℃ for reaction for 6h until the water yield is not lower than 95% of the theoretical value, and cooling to 150 ℃; adding 10 parts of maleic anhydride, and reacting for 5 hours under the condition of heat preservation until the acid value is 2-30 mgKOH/g; cooling to room temperature, and washing with anhydrous ethanol for 3 times; drying for 3h at 60 ℃ to obtain the modified crystal polyester resin.
2) Taking 15 parts of aluminum nitride CW-AlN-001 (Shanghai ultra-micro nano) and heating to 1000 ℃ and preserving heat for 3 hours; after cooling to room temperature, adding aluminum nitride and 0.15 part of silane coupling agent KH-550 into an alcohol solvent, and mechanically stirring for 6 hours to form a mixed solution; ball milling is carried out for 4h by using a ball mill, after suction filtration, absolute ethyl alcohol is used for repeatedly washing, and the mixture is put into a 60 ℃ oven for drying for 3h to obtain the modified aluminum nitride.
3) And (2) adding 40 parts of the modified crystal form polyester resin obtained in the step 1) and 5 parts of TAR-3350-50 acrylic resin (Shenzhen Jiashenda) into 40 parts of toluene and 30 parts of butanone solution, and mechanically stirring for 3 hours until the modified crystal form polyester resin and the TAR-3350-50 acrylic resin are completely dissolved.
4) Adding 9 parts of #10 insulating carbon black (Mitsubishi, Japan), 15 parts of modified aluminum nitride in the step 2) and 1 part of wetting dispersant D-2013(BYK) into the resin solution in the step 3), and mechanically stirring for 1 hour.
5) And (3) taking the mixture obtained in the step 4), putting the mixture into a sand mill, sanding for 3 hours, and filtering with 400-mesh filter cloth to obtain the component A of the ink.
6) And (3) taking 50 parts of the ink A component in the step 5), adding 60 parts of butanone serving as a solvent and 3 parts of isocyanate curing agent N-3390 (Bayer) serving as the ink B component, and mechanically stirring for 30min to obtain the well-dispersed heat-conducting insulating ink.
The basic properties of the thermally conductive and insulating ink and the thermally conductive and insulating ink printed layer are detailed in table 1.
Table 1 properties of the thermally conductive and insulating ink and the thermally conductive and insulating ink printed layer.
Figure 667385DEST_PATH_IMAGE001
。
The basic performance test result shows that the heat-conducting insulating ink prepared by directly adding the heat-conducting filler into the amorphous resin and then sanding with other components in the comparative example 1 has low stability and low heat conductivity coefficient; in comparative example 2, the modified crystal-form resin is matched with the heat-conducting filler to improve the heat conductivity of the ink printing layer, but the crystal-form resin has higher brittleness and poorer flexibility; in the embodiments 1, 2, 3 and 4, the maleic anhydride modified crystal-form resin is used and then matched with the amorphous resin, and the modified heat-conducting filler is added, so that the compatibility of the filler and the resin can be obviously improved, the stability is high, a heat-conducting path is easily formed after drying, the heat conductivity of a printing layer is improved, and the adhesive force of the printing ink to a copper foil is enhanced; in addition, as can be seen from example 1, the polybasic acid and the polyhydric alcohol which adopt the polymethylene have high crystallization degree and stronger thermal conductivity; by comparing examples 1, 3 and 4 with example 2, the thermal conductivity of the crystalline polyester resin is better than that of the crystalline polypropylene resin.
In conclusion, compared with the heat-conducting insulating ink prepared by the invention and the application of the heat-conducting insulating ink on the copper foil tape, the heat-conducting insulating ink prepared by the invention has the advantages of good stability, high heat conductivity coefficient of an ink printing layer, small roughness, good insulativity, good adhesive force of the ink printing layer on the copper foil surface and high surface energy, and is very suitable for being applied to 3C products.
The properties of the thermally conductive and insulating ink and the ink printed layer were tested by the following instruments.
1. The viscosity test is carried out by adopting an NDJ-5S rotational viscometer of Shanghai Changji geological instruments GmbH.
2. The surface energy was measured using a schumann dyne pen in the uk.
3. The adhesion force was measured by a grid cutting instrument manufactured by macke instruments ltd, guan, inc.
4. The fineness test adopts a Tianjin Yonglida scraper fineness tester for testing.
5. The roughness test is carried out by adopting a Japan Sanfeng SJ-210 roughness tester.
6. The heat conductivity test adopts Hunan instrument DRE-III multifunctional rapid heat conductivity tester.
7. The volume resistivity test adopts a ZST-121 surface volume resistivity tester for testing in the middle aviation age.
8. The flexibility test was according to GB/T1731-93.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (9)

1. A heat-conducting insulating ink comprises a component A and a component B, and is characterized in that:
the component A comprises the following raw materials in parts by mass:
30-40 parts of modified crystalline resin, 5-10 parts of amorphous resin, 8-10 parts of pigment, 10-15 parts of modified heat-conducting filler, 1-2 parts of auxiliary agent and 70-80 parts of solvent;
the modified crystal-form resin is at least one of modified crystal-form polyester resin and modified crystal-form polypropylene resin, the number average molecular weight is 80000-300000, the softening point is 100-150 ℃, and the acid value is 2-30 mgKOH/g;
the amorphous resin is at least one of amorphous polyester resin, amorphous epoxy resin, amorphous polyurethane resin, amorphous polyamide resin, amorphous acrylic resin and amorphous alkyd resin, the number average molecular weight is 20000-40000, the softening point is 20-90 ℃, and the hydroxyl value is 3-10 mgKOH/g;
the modified heat-conducting filler is at least one of boron nitride, aluminum nitride, silicon nitride and silicon carbide modified by ultrasonic waves or a coupling agent;
the component B is an isocyanate curing agent, and the using amount of the component B accounts for 4-10% of the mass ratio of the component A.
2. The thermally conductive and insulating ink of claim 1, wherein:
the modified crystal polyester resin is obtained by performing polycondensation on at least one of polyhydric alcohols neopentyl glycol, 1, 6-hexanediol, trimethylolpropane, diethylene glycol, 1, 4-cyclohexanediol and 1, 4-butanediol and at least one of polybasic acid adipic acid, 1, 12-dodecanedioic acid, succinic acid, itaconic acid, 1, 4-cyclohexanedicarboxylic acid and terephthalic acid to obtain a prepolymer and modifying the prepolymer with maleic anhydride;
the modified crystal form polypropylene resin is obtained by blending and melting polypropylene resin and β -nucleating agent to obtain a prepolymer and then modifying the prepolymer with maleic anhydride.
3. The thermally conductive and insulating ink of claim 1, wherein: the ultrasonic modified heat-conducting filler is obtained by adding the heat-conducting filler after annealing treatment into at least one of alcohol solvents such as absolute ethyl alcohol, isopropanol and n-butanol and carrying out ultrasonic treatment; the coupling agent modified heat-conducting filler is surface modified by adding at least one of silane coupling agent, titanate coupling agent and aluminate coupling agent.
4. The thermally conductive and insulating ink of claim 1, wherein: the pigment is at least one of insulating carbon black and barium sulfate.
5. The thermally conductive and insulating ink of claim 2, wherein:
the preparation method of the modified crystal polyester resin comprises the following steps:
1) adding polyalcohol and polybasic acid into a reaction container, mixing for 1-1.5 h at 60-80 ℃, gradually heating to 180-240 ℃ for reaction for 2-6 h until the water yield is not lower than 95% of a theoretical value, and cooling to 150 ℃;
2) adding maleic anhydride, and reacting for 3-5 h under the condition of heat preservation until the acid value is 2-30 mgKOH/g;
3) cooling to room temperature, and diluting with absolute ethyl alcohol for 2-4 times;
4) drying for 2-3 h at 60 ℃;
the modified crystal form polypropylene resin comprises the following steps:
1) adding polypropylene and β -nucleating agent into a container, heating to 150-200 ℃, melting for 3-5 hours at high temperature until the molecular weight is 80000-200000, and cooling to 150 ℃;
2) adding maleic anhydride, and reacting for 3-5 h under the condition of heat preservation until the acid value is 2-30 mgKOH/g;
3) cooling to room temperature, and diluting with absolute ethyl alcohol for 2-4 times;
4) drying for 2-3 h at 60 ℃.
6. The thermally conductive and insulating ink of claim 3, wherein:
the ultrasonic modified heat-conducting filler comprises the following steps:
1) heating the heat-conducting filler to 1000 ℃ and preserving heat for 2-3 h;
2) naturally cooling to room temperature, and then putting the mixture into an alcohol solvent for ultrasonic treatment for 5-8 hours to form heat-conducting filler slurry;
3) filtering the heat-conducting filler slurry obtained in the step 2), and repeatedly washing with absolute ethyl alcohol for 2-3 times;
4) drying the mixture in an oven at the temperature of 60-80 ℃ for 2-3 hours to obtain the modified heat-conducting filler;
the coupling agent modified heat-conducting filler comprises the following steps:
1) heating the heat-conducting filler to 1000 ℃ and preserving heat for 2-3 h;
2) naturally cooling to room temperature, adding the heat-conducting filler and the coupling agent into the alcohol solvent, and mechanically stirring for 3-6 hours to form a mixed solution;
3) ball-milling the mixed solution in the step 2) for 2-4 h by using a ball mill;
4) filtering the mixed solution in the step 3), and repeatedly washing the mixed solution for 2-3 times by using absolute ethyl alcohol;
5) and drying the mixture in an oven at the temperature of 60-80 ℃ for 2-3 hours to obtain the modified heat-conducting filler.
7. The method for preparing a heat conductive insulating ink according to any one of claims 1 to 6, wherein:
the heat-conducting and insulating ink comprises the following steps:
1) adding the modified crystalline resin, the amorphous resin and a solvent into a container, and mechanically stirring for 2-3 hours until the resin is completely dissolved;
2) adding the modified heat-conducting filler, the pigment and the auxiliary agent into the resin solution and stirring for 1-2 h;
3) sanding for 2-4 h by using a sand mill until the particle size fineness is less than 3 mu m;
4) filtering with 400 mesh filter cloth to obtain component A;
5) and (3) adding the component B into the component A in the step 4) to obtain the heat-conducting and insulating ink.
8. The application of the heat-conducting insulating ink in the copper foil tape as claimed in one of claims 1 to 6, wherein the following raw materials are uniformly mixed and printed on the surface of the copper foil tape in parts by mass:
50-60 parts of a heat-conducting and insulating ink component A, 60-70 parts of an organic solvent and a component B isocyanate curing agent, wherein the content of the isocyanate curing agent in the component A is 4-10%.
9. The use of the thermally conductive and insulating ink according to claim 8 in copper foil tape, wherein: the heat conductivity coefficient of the heat-conducting insulating ink printed on the copper foil after being dried is more than or equal to 4W/(M.K), the surface energy is more than or equal to 46mN/M, the roughness is less than or equal to 3 mu M, and the volume resistivity is 1013~16Omega cm, the adhesive force level of the copper foil surface printing layer is 5B.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112375424A (en) * 2020-10-27 2021-02-19 安徽省粤隆印刷科技有限公司 Water-based ink-based packaging box green printing process
CN114479549A (en) * 2022-03-23 2022-05-13 广州亦盛环保科技有限公司 Multilayer graphene oxide heat dissipation insulation ink and preparation method thereof
CN114621615A (en) * 2021-12-27 2022-06-14 盐城九智新材料科技有限公司 Coating material for electronic heat dissipation film and preparation process thereof
CN115851031A (en) * 2022-12-23 2023-03-28 深圳稀导技术有限公司 Heat-dissipation printing ink

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101405662A (en) * 2006-03-14 2009-04-08 株式会社理光 Toner for developing electrostatic charge image and image forming device using the same
WO2009108304A1 (en) * 2008-02-26 2009-09-03 Cambrios Technologies Corporation Methods and compositions for ink jet deposition of conductive features
CN101787178A (en) * 2010-03-09 2010-07-28 王全胜 Heat-conduction electric insulation composite material component and manufacturing method thereof
CN102212273A (en) * 2011-04-29 2011-10-12 上海安美特铝业有限公司 Heat-conducting material used for solar photoelectricity-heat conversion equipment and preparation method thereof
CN102711421A (en) * 2012-06-28 2012-10-03 东莞市群跃电子材料科技有限公司 Shielded radiating material structure and manufacturing method
CN102887993A (en) * 2011-07-19 2013-01-23 上海涂料有限公司技术中心 Preparation method of waterborne polyester resin used in coil coatings and application thereof
CN204733501U (en) * 2015-04-30 2015-10-28 昆山雅森电子材料科技有限公司 There is the fin of Electromagnetic Interference function of shielding
WO2016090859A1 (en) * 2014-12-11 2016-06-16 广东生益科技股份有限公司 Thermosetting resin composition for degradable heat-conducting aluminum-based copper-clad plate, heat-conducting aluminum-based copper-clad plate, and preparation method and recovery method thereof
CN106928838A (en) * 2017-03-30 2017-07-07 东莞市万丰纳米材料有限公司 A kind of heat-dissipation paint
CN107540959A (en) * 2017-09-08 2018-01-05 湖北祥源新材科技股份有限公司 A kind of multifunctional bubble cotton piece material and preparation method thereof
EP3323795A1 (en) * 2015-09-16 2018-05-23 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Alumina-based heat conductive oxide and method for producing same
US20180298215A1 (en) * 2015-10-09 2018-10-18 Syddansk Universitet Feedstock for 3d printing and uses thereof
CN109575551A (en) * 2017-09-29 2019-04-05 中国石油化工股份有限公司 Modified resin and its preparation method and application for heat conduction and heat radiation
CN110343419A (en) * 2019-07-25 2019-10-18 深圳市至臻精密股份有限公司 A kind of high heat conductive insulating polyimide ink and preparation method thereof

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101405662A (en) * 2006-03-14 2009-04-08 株式会社理光 Toner for developing electrostatic charge image and image forming device using the same
WO2009108304A1 (en) * 2008-02-26 2009-09-03 Cambrios Technologies Corporation Methods and compositions for ink jet deposition of conductive features
CN101787178A (en) * 2010-03-09 2010-07-28 王全胜 Heat-conduction electric insulation composite material component and manufacturing method thereof
CN102212273A (en) * 2011-04-29 2011-10-12 上海安美特铝业有限公司 Heat-conducting material used for solar photoelectricity-heat conversion equipment and preparation method thereof
CN102887993A (en) * 2011-07-19 2013-01-23 上海涂料有限公司技术中心 Preparation method of waterborne polyester resin used in coil coatings and application thereof
CN102711421A (en) * 2012-06-28 2012-10-03 东莞市群跃电子材料科技有限公司 Shielded radiating material structure and manufacturing method
WO2016090859A1 (en) * 2014-12-11 2016-06-16 广东生益科技股份有限公司 Thermosetting resin composition for degradable heat-conducting aluminum-based copper-clad plate, heat-conducting aluminum-based copper-clad plate, and preparation method and recovery method thereof
CN204733501U (en) * 2015-04-30 2015-10-28 昆山雅森电子材料科技有限公司 There is the fin of Electromagnetic Interference function of shielding
EP3323795A1 (en) * 2015-09-16 2018-05-23 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Alumina-based heat conductive oxide and method for producing same
US20180298215A1 (en) * 2015-10-09 2018-10-18 Syddansk Universitet Feedstock for 3d printing and uses thereof
CN106928838A (en) * 2017-03-30 2017-07-07 东莞市万丰纳米材料有限公司 A kind of heat-dissipation paint
CN107540959A (en) * 2017-09-08 2018-01-05 湖北祥源新材科技股份有限公司 A kind of multifunctional bubble cotton piece material and preparation method thereof
CN109575551A (en) * 2017-09-29 2019-04-05 中国石油化工股份有限公司 Modified resin and its preparation method and application for heat conduction and heat radiation
CN110343419A (en) * 2019-07-25 2019-10-18 深圳市至臻精密股份有限公司 A kind of high heat conductive insulating polyimide ink and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YOSHIHARA, S: "Main- Chain Smectic Liquid Crystalline Polymer Exhibiting Unusually High Thermal Conductivity in an Isotropic Composite", 《JOURNAL OF APPLIED POLYMER SCIENCE》 *
石路晶: "导热高分子材料在电子封装领域应用研究", 《包装工程》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112375424A (en) * 2020-10-27 2021-02-19 安徽省粤隆印刷科技有限公司 Water-based ink-based packaging box green printing process
CN112375424B (en) * 2020-10-27 2022-04-15 安徽省粤隆印刷科技有限公司 Water-based ink-based packaging box green printing process
CN114621615A (en) * 2021-12-27 2022-06-14 盐城九智新材料科技有限公司 Coating material for electronic heat dissipation film and preparation process thereof
CN114479549A (en) * 2022-03-23 2022-05-13 广州亦盛环保科技有限公司 Multilayer graphene oxide heat dissipation insulation ink and preparation method thereof
CN115851031A (en) * 2022-12-23 2023-03-28 深圳稀导技术有限公司 Heat-dissipation printing ink

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