WO2016047988A1 - Nitrure de bore modifié en surface, composition ayant des particules de celui-ci dispersées en son sein, et câble revêtu de la composition - Google Patents

Nitrure de bore modifié en surface, composition ayant des particules de celui-ci dispersées en son sein, et câble revêtu de la composition Download PDF

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WO2016047988A1
WO2016047988A1 PCT/KR2015/009910 KR2015009910W WO2016047988A1 WO 2016047988 A1 WO2016047988 A1 WO 2016047988A1 KR 2015009910 W KR2015009910 W KR 2015009910W WO 2016047988 A1 WO2016047988 A1 WO 2016047988A1
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boron nitride
group
modified
silane
nitride particles
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PCT/KR2015/009910
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English (en)
Korean (ko)
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서영수
박건우
하승훈
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세종대학교산학협력단
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Publication of WO2016047988A1 publication Critical patent/WO2016047988A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/14—Compounds containing boron and nitrogen, phosphorus, sulfur, selenium or tellurium
    • 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
    • C08K3/38—Boron-containing compounds
    • 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
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • the present invention relates to surface modified inorganic particles, and more particularly, to surface modified boron nitride particles, a composition in which the particles are dispersed, and a wire coated with the composition.
  • Thermally conductive materials are showing an increasing trend in their range of use and usage due to the higher integration of electronic components and products and increased power consumption.
  • Thermally conductive materials including existing metals, have made great efforts to replace metal composites using materials having high formability and productivity due to low formability and productivity. Therefore, in order to increase the thermal conductivity and injection moldability, it is used to replace a certain portion of the metal by using a composite made of a thermal conductive filler such as ceramic, carbon, and a polymer.
  • Heat transfer from ceramics to electrical insulators is caused primarily by lattice vibrations by phonons instead of free electrons, and the phonon scattering is induced by thermal resistance, which is related to the presence of a thermal barrier between the matrix and the filler. Therefore, research is being conducted to increase the mobility of phonons by suppressing scattering.
  • the thermally conductive fillers in the matrix can be formed to form a continuous network or large particles can be used to reduce the number of thermal resistance bonds between adjacent filler particles.
  • a filler may be used or a type of filler that reduces the thermal contact resistance between the thermally conductive fillers.
  • fillers with various particle size distributions and using polymers with low melt viscosity to improve interfacial adhesion and wettability of the filler and polymer matrix reduces the possibility of void formation in the polymer composites. Although effective in improving the thermal conductivity, there is a problem that is not applied when the compatibility between the polymer and the filler is not good.
  • Boron nitride having a layered structure is excellent in thermal conductivity, but due to its plate shape, there is a problem that aggregation can occur well with each other, so it is difficult to use as a thermally conductive material.
  • the problem to be solved by the present invention is to provide a surface-modified boron nitride to improve the dispersibility.
  • Another object of the present invention is to provide a coating composition containing a surface-modified boron nitride.
  • Another problem to be solved by the present invention is to provide an electronic component having a coating layer containing a surface-modified boron nitride.
  • One aspect of the present invention to achieve the above object provides a multi-surface modified boron nitride. It comprises boron nitride particles, a first surface modifier bonded to the surface of the boron nitride particles and containing an aromatic group at the terminal, and a second surface modifier bonded to the surface of the boron nitride particles and containing an amine group or an epoxy group at the terminal. do.
  • the surface modifiers are silane compounds and may be bonded to the surface of the boron nitride particles by siloxane bonds.
  • the boron nitride particles may be a plate-shaped hexagonal boron nitride.
  • the aromatic group of the first surface modifier is a phenyl group, an anilinyl group, a benzoyl group, a phenoxy group, a biphenyl group, or a naphthalenyl group.
  • the first surface modifier is trimethoxyphenylsilane, N- [3- (trimethoxysilyl) propyl] aniline, allylphenyldichlorosilane, aminophenyltrimethoxysilane, t-butylphenyldichlorosilane, p- (t -Butyl) phenethyltrichlorosilane, 3,5-dimethoxyphenyltriethoxysilane, diphenyldiethoxysilane, diphenyldimethoxysilane, diphenylmethylethoxysilane, 3- (p-methoxyphenyl) propyl Trichlorosilane, p-methoxyphenyltrimethoxy
  • the amine group of the second surface modifier may be a primary amine group, a secondary amine group, a tertiary amine group, or a diamine group.
  • the second surface modifier is 3- [2- (2-aminoethylamino) ethylamino] propyltrimethoxysilane, N- [3- (trimethoxysilyl) propyl] ethylenediamine, (3-aminopropyl) tri Methoxysilane, and combinations thereof.
  • the second surface modifier may be N- [3- (trimethoxysilyl) propyl] ethylenediamine having a diamine group at its terminal.
  • the epoxy of the second surface modifier may be an epoxide group, glycidyl group, or glycidyloxy group.
  • the second surface modifier is 3-epoxypropyltrimethoxysilane, 3-epoxypropyltriethoxysilane, 4-epoxybutyltrimethoxysilane, 4-epoxybutyltriethoxysilane, 3-glycidyloxypropyltri Methoxysilane, and combinations thereof.
  • the second surface modifier may be 3-glycidyloxypropyltrimethoxysilane having a glycidyloxy group at the terminal.
  • a third surface modifier containing an alkyl group at the terminal may be further bonded to the surface of the boron nitride particles.
  • the coating composition includes 100 parts by weight of the polymer or polymer precursor, 1 to 80 parts by weight of the multi-surface modified boron nitride as described above, and the balance of the solvent.
  • the polymer precursor is epoxy resin, phenol resin, polyester, polyesterimide, polyesteramide, polyesteramideimide, (tri (2-hydroxyethyl) isocyanuate triacrylate) -polyesterimide, polyether It may be selected from the group consisting of mid, polyamide, polyamideimide, polyimide, polyurethane, polyvinyl formal, and combinations thereof.
  • a wire It comprises a conductive wire and a thermally conductive film formed on the conductive wire.
  • the thermally conductive film contains a polymer matrix and a multi-surface modified boron nitride as described above dispersed in the polymer matrix.
  • the polymer matrix is polyester, polyesterimide, polyesteramide, polyesteramideimide, (tri (2-hydroxyethyl) isocyanuate triacrylate) -polyesterimide, polyetherimide, polyamide, poly Amideimide, polyimide, polyurethane, polyvinyl formal, epoxy resin, phenol resin, and combinations thereof.
  • an internal insulating discharge layer including an organic insulating polymer matrix and an inorganic nanofiller dispersed in the organic insulating polymer matrix may be disposed.
  • the inorganic nanofiller may be selected from the group consisting of silica, titania, alumina, zirconia, yttria, chromium oxide, zinc oxide, iron oxide, clay, and combinations thereof.
  • the boron nitride particles are plate-shaped particles, and the plate-like surface of the boron nitride particles may face the conductive wire.
  • the plate-like surface of the boron nitride particles and the surface of the conductive wire may be parallel.
  • An angle between the plate surface of the boron nitride particles and the surface of the conductive wire may be smaller than an angle between the plate surface of the boron nitride particles and the waterline perpendicular to the surface of the conductive wire.
  • the surface modifier occupies the surface of the boron nitride by modifying the surface of the boron nitride by using a surface modifier having an aromatic group at the terminal and a surface modifier having an amine group or an epoxy group at the terminal.
  • a surface modifier having an aromatic group at the terminal and a surface modifier having an amine group or an epoxy group at the terminal.
  • dispersibility can be greatly improved in the polymer solution or the polymer matrix.
  • the aromatic group and the amine group or the epoxy group may exhibit strong interaction with the polymer and the solvent in the polymer solution and the polymer in the polymer matrix, and thus dispersibility may be maintained.
  • FIG. 1 is a schematic view showing a surface-modified boron nitride according to one embodiment of the present invention.
  • FIG. 2A is a schematic view showing a cross section of a wire according to an embodiment of the present invention
  • FIG. 2B is an enlarged cross-sectional view of part B of FIG. 2A.
  • Figure 3a is a photograph of the fracture surface of the boron nitride (20 wt%)-PAI complex according to Experimental Example 1
  • Figure 3b is a boron nitride (20 wt%)-PAI complex of Comparative Example 2 A photograph of the fracture surface observed with a scanning microscope.
  • Figure 4a is a photograph of the fracture surface of the boron nitride-epoxy composite according to Experimental Example 2 with a scanning electron microscope
  • Figure 4b is a photograph of a fracture surface of the boron nitride-epoxy composite according to Comparative Example 7 with a scanning microscope .
  • a layer is located on another layer may mean that not only are these layers directly in contact, but also another layer (s) between these layers.
  • FIG. 1 is a schematic view showing a surface-modified boron nitride according to one embodiment of the present invention.
  • the boron nitride particles BN may be amorphous boron nitride, crystalline boron nitride, or a complex thereof.
  • boron nitride (BN) may be hexagonal boron nitride (hexagonal BN) having a crystal structure similar to graphite.
  • hexagonal BN hexagonal boron nitride
  • boron nitride (BN) may have a structure in which hexagonal mesh layers are stacked in multiple layers, or may be made of a single layer, and may be plate-shaped particles.
  • Such plate-like boron nitride may have a particle diameter of about 0.1 to about 20 ⁇ m, specifically 0.3 to about 5 ⁇ m, more specifically 0.3 to about 1 ⁇ m, and also about 1 nm to about 3 ⁇ m, or It may have a particle thickness of about 10 nm to about 500 nm, or about 10 nm to about 200 nm, or about 10 nm to about 100 nm, or about 10 nm to about 30 nm.
  • the particle diameter or the particle thickness may be an average value of several particles.
  • the plate-like boron nitride (BN) may have a ratio of particle diameter to thickness, that is, an aspect ratio of 1: 10 to 1: 100, specifically 1: 30 to 1: 70.
  • the plate-like boron nitride (BN) has a large surface energy (surface energy) in the side compared to the upper and lower surfaces, that is, the plate-like surface corresponding to the surface of the mesh layer may be low in stability.
  • such plate-like boron nitride (BN) may have more reaction sites on the side, that is, hydroxyl groups, than the upper and lower sides.
  • first and second surface modifiers S 1 and S 2 may be provided.
  • a third surface modifier S 3 may additionally be provided.
  • the surface modifiers S 1 , S 2 , and S 3 may include a head group, a terminal functional group, and a tail portion connecting the head group and the terminal functional group to the boron nitride. part).
  • the tail portion may be an alkyl group of C1 to C10 (C1, C2, C3, C4, C5, C6, C7, C8, C9, C10), specifically C1 to C6, more specifically C1 to C4.
  • one or more -CH 2 -of the alkyl group may be substituted with -NH-.
  • the present invention is not limited thereto, and the tail portion may be omitted, particularly when the terminal functional group is an alkyl group.
  • the surface modifiers S 1 , S 2 , S 3 may each be a silane having a silane group substituted with a silane group, specifically, 1, 2 or 3 substituents as a head group.
  • the substituent (s) of the silane group may be a hydroxyl group, an alkoxy group, a halo group, or a combination thereof.
  • the surface modifiers (S 1 , S 2 , S 3 ) are each a headalkoxy silane group, dialkoxy silane group, alkoxy silane group, dialkoxyhalo silane group, alkoxydihalo silane as head group.
  • a group, a trihalo silane group, a dihalosilane group, and a halosilane group can be provided.
  • the alkoxy group may be a methoxy group or an ethoxy group
  • the halo group may be a chloro group.
  • silane groups react with reaction sites, for example, hydroxyl groups, on the sides rather than on the upper and lower sides of the plate-like boron nitride (BN) to bond with boron nitride (BN), for example, to siloxane bonds. Can be combined.
  • Each surface modifier (S 1 , S 2 , S 3 ) may have different terminal functional groups.
  • the first surface modifier S 1 may include an aromatic group R 1 as a terminal functional group.
  • the aromatic group may be substituted or unsubstituted, and may be a phenyl group, an anilinyl group, a benzoyl group, a phenoxy group, a biphenyl group, or a naphthalene group ( naphthalenyl group).
  • Substituents for the aromatic groups may be C1, C2, C3 or C4 alkyl groups, C1, C2, or C3 alkoxy groups, C2, or C3 allyl groups, amine groups, hydroxyl groups, or halogen groups.
  • the aromatic group of the first surface modifier (S 1 ) may be a substituted or unsubstituted ananilinyl group, and further may be an unsubstituted anilinyl group.
  • the first surface modifier (S 1 ) having an aromatic group as a terminal functional group is trimethoxyphenylsilane, N- [3- (trimethoxysilyl) propyl] aniline (N- [3- (trimethoxysilyl) propyl aniline), allylphenyldichlorosilane, aminophenyltrimethoxysilane, t-butylphenyldichlorosilane, p- (t-butyl) phenethyltrichlorosilane (p- ( t-butyl) phenethyltrichlorosilane), 3,5-dimethoxyphenyltriethoxysilane, diphenyldiethoxysilane, diphenyldimethoxysilane, diphenylmethylethoxysilane (diphenylmethylethoxysilane), 3- (p-methoxyphenyl) propyltrichlorosilane, 3- (pmeth
  • the second surface modifier (S 2 ) may have an amine group or an epoxy group (R 2 ) as the terminal functional group.
  • the amine group (R 2 ) may be substituted or unsubstituted, but may be a primary amine group, a secondary amine group, a tertiary amine group, or a diamine group, but is not limited thereto.
  • the diamine group may be ethylenediamine, propanediamine, or butanediamine.
  • the second surface modifier (S 2 ) having an amine group (R 2 ) is 3- [2- (2-aminoethylamino) ethylamino] propyltrimethoxysilane, N- [3- (trimethoxysilyl) propyl ] Ethylenediamine, (3-aminopropyl) trimethoxysilane, and combinations thereof, but is not limited thereto.
  • the epoxy group (R 2 ) may be an epoxide group, glycidyl group, or glycidyloxy group.
  • a first surface modifying agent having an epoxy group such a (R 2) group as a terminal functional (S 2) is, in particular, 3-epoxy-trimethoxysilane, 3-in-epoxypropyl triethoxysilane, 4-epoxy-butyl trimethoxysilane Methoxysilane, 4-epoxybutyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, and combinations thereof.
  • the third surface modifier S 3 may have an alkyl group R 3 as a terminal functional group. As described above, in this case, the tail portion may be omitted.
  • the alkyl group (R 3 ) may be an alkyl group of 1 to C10 (C1, C2, C3, C4, C5, C6, C7, C8, C9, C10), specifically C1 to C6, more specifically C1 to C4 have.
  • the third surface modifier (S 3 ) is ethyltrimethoxysilane, methoxytrimethylsilane, ethoxytrimethylsilane, triethylchlorosilane, trimethylchlorosilane ), Heptyltrimethoxysilane, and combinations thereof.
  • the surface-modified specifically silane surface-modified boron nitride 35 may include the first to third surface modifiers S 1 , S 2 , and S 3 , that is, the first silane, the second silane, and the third silane. Additional surface modifiers For example, silanes may be chemically bonded to the surface of the boron nitride (BN), but is not limited thereto.
  • the surface-modified boron nitride 35 may be powder, gel, or liquid, but is not limited thereto.
  • the first surface-modifying agent (S 1) and the second surface modifier third surface modifying agent (S 3) having an alkyl group (R 3) between (S 2) as the group terminal function may be disposed.
  • the terminal functional groups are smaller in order of aromatic group, amine group or epoxy group, and alkyl group. As such, surface modifiers having relatively small terminal functional groups may be disposed between surface modifiers having relatively large terminal functional groups.
  • the method of surface modifying boron nitride using a multiple surface modifier may be as follows.
  • the boron nitride powder may be mixed in a solvent to form a mixed solution. Ultrasonic waves may be added to the mixed solution.
  • the boron nitride (BN) can be peeled off, i.e., layered, to have a thinner thickness, and can also generate more reaction sites (ex. -OH) on the surface, especially the side, of the boron nitride (BN). .
  • the boron nitride (BN) may be further exfoliated and may have more reaction sites, and at the same time, may be bonded to the first silane (S 1 ) by a siloxane bond.
  • boron nitride (BN) surface-modified by the first silane (S 1 ) can be obtained.
  • a second silane (S 2 ) containing an amine group or an epoxy group (R 2 ) may be added and ultrasonic waves may be added.
  • the boron nitride (BN) may be further peeled off and may have more reaction sites, and may be bonded to the second silane (S 2 ) by siloxane bonds.
  • the boron nitride 35 surface-modified by the first silane S 1 and the second silane S 2 may be obtained.
  • the boron nitride 35 surface-modified by the first to third silanes (S 1 , S 2 , S 3 ) can be obtained.
  • the surface-modified boron nitride 35 dispersed in the solvent may be filtered and washed to remove the unreacted silane.
  • the washed solid may be dried to obtain a boron nitride powder surface modified by multiple silanes.
  • the present invention is not limited thereto, and the silane surface-modified boron nitride 35 may be obtained in a sol form, a gel form, or a liquid phase dispersed in a solvent phase.
  • the terminal functional group of the first silane (S 1 ), that is, the aromatic group (R 1 ) is larger than the terminal functional group of the second silane (S 2 ), that is, the amine group or the epoxy group (R 2 ).
  • the first silane (S 1 ) on the surface of the boron nitride may be somewhat sparsely coupled.
  • the first silane to the second silane (S 2) having a small terminal features compared to (S 1) the first can be easily accessed and coupled to remaining reactive sites between the silane of (S 1).
  • the terminal functional group of the third silane (S 3 ), that is, the alkyl group (R 3 ) is smaller than those of the first silane (S 1 ) and the second silane (S 2 ) (R 1 , R 2 ). .
  • the third silane S 3 can be easily accessed and coupled to the remaining reaction site between the first silanes S 1 and the second silane S 2 .
  • different types of silanes having different sized terminal functional groups are used, but silanes having larger sized functional groups are first reacted with boron nitride or at the same time having smaller sized functional groups.
  • At least one second silane (S 2 ) having an amine group or an epoxy group (R 2 ) as a terminal functional group may be disposed between the).
  • a third silane (S 3 ) having an alkyl group (R 3 ) as a terminal functional group may be disposed between the first silane (S 1 ) and the second silane (S 2 ).
  • boron nitride having an improved surface occupancy by silane may exhibit greatly improved dispersibility with respect to a polymer solution or a polymer matrix described later.
  • the solvent may be a polar solvent, for example, toluene, xylene, ethanol, methanol, cresol, water, acetone, cyclohexane, phenol, N-methylpyrolidone (NMP), glycol ether, N, N-dimethylformamide (N, N-Dimethylformamide, DMF), and combinations thereof may be included, but is not limited thereto.
  • a polar solvent for example, toluene, xylene, ethanol, methanol, cresol, water, acetone, cyclohexane, phenol, N-methylpyrolidone (NMP), glycol ether, N, N-dimethylformamide (N, N-Dimethylformamide, DMF), and combinations thereof may be included, but is not limited thereto.
  • the process of irradiating the ultrasonic wave may have an advantage of shortening the time required compared to the surface treatment process performed using only the heat and the solvent of the prior art, but is not limited thereto.
  • the surface treatment time required to secure surface coverage showing satisfactory dispersibility with respect to the polymer solution or the polymer matrix can be shortened through the sonication.
  • the bath ultrasonic treatment may take about 3 days, and in the case of horn ultrasonic treatment, the surface treatment may be performed.
  • the time required can be dramatically shortened to about 3.5 hours.
  • the coating composition in which the surface-modified boron nitride is dispersed in multiple silanes may include 100 parts by weight of a polymer or polymer precursor, 1 to 200 parts by weight of surface-modified boron nitride, and the balance of It may include a solvent.
  • the boron nitride may be surface-modified with the first and second silanes, additionally with the third silane, as described in the first embodiment. For example, 1 to 80 parts by weight, 10 to 70 parts by weight, and 10 to 50 parts by weight. 20 to 30 parts by weight, 20 to 60 parts by weight, or 30 to 50 parts by weight.
  • the polymer precursor may be a polymerizable material and may be a monomer, an oligomer having a few to several tens of monomers, or a prepolymer.
  • the polymer precursor may be a prepolymer, wherein the prepolymer is polyester (ex. Polyethylene terephthalate), polyesterimide, polyesteramide, polyesteramideimide, (tri (2-hydroxyethyl) isocy Anuate triacrylate) -polyesterimide, polyetherimide, polyamide, polyamideimide, polyimide, polyurethane, polyvinyl formal, epoxy resin, phenolic resin, and combinations thereof It may include, but is not limited thereto.
  • the polymer precursor may include an aromatic group, an epoxy group, or a combination thereof in the main chain thereof.
  • the prepolymer may be a polyesterimide represented by the following formula (1).
  • n 2 to 99
  • m is an integer of 1 to 4.
  • the prepolymer may be a polyamideimide represented by the following formula (2).
  • n is an integer of 2 to 99.
  • the solvent is a group consisting of toluene, xylene, ethanol, methanol, cresol, water, acetone, cyclohexane, phenol, N-methylpyrrolidone, glycol ether, N, N-dimethylformamide, and combinations thereof. It may include, but is not limited to selected from.
  • the solvent may further include, but is not limited to, a diluent used to dilute the composition.
  • the mixture of the polymer precursor and the solvent may be a varnish.
  • 'Varnish' means a paint forming a coating film.
  • boron nitride surface modified with the first and second silanes, additionally with the third silane may exhibit high dispersibility in the composition due to the high surface occupancy of the silane modifiers.
  • the aromatic group, which is the terminal functional group of the first silane may exhibit strong interaction with the polymer precursor, particularly the polymer precursor having the aromatic group, and also due to the amine group, which is the terminal functional group of the second silane, the solvent, for example, N- Strong interactions can also be shown for solvents with amine groups such as methylpyrrolidone.
  • the dispersibility of the boron nitride surface-modified with the multiple silanes in the composition can be further improved.
  • the organic insulating polymer is polyester, polyester imide, polyester amide, polyester amide imide, (tri (2-hydroxy ethyl) isocyanuate triacrylate)-polyester imide, poly ether imide, polyamide , Polyamideimide, polyimide, polyurethane, polyvinyl formal, and combinations thereof may be included, but is not limited thereto.
  • the inorganic nanofiller 25 may include one selected from the group consisting of silica, titania, alumina, zirconia, yttria, chromium oxide, zinc oxide, iron oxide, clay, and combinations thereof, but is not limited thereto. It is not.
  • the silica may be fumed silica, but may be fused silica, precipitated silica, silica prepared by a sol-gel method, or colloidal silica, but is not limited thereto.
  • the titania may be fumed titania, but may be molten titania, precipitated titania, titania produced by the sol-gel method, or colloidal titania, but is not limited thereto.
  • the alumina may be fumed alumina, fused alumina, precipitated alumina, alumina prepared by the sol-gel method, or colloidal alumina, but is not limited thereto.
  • the inorganic nanofiller 25 may also be surface modified by a silane modifier. Specifically, the surface of the inorganic nanofiller 25 is a surface-modified chemical bond between the first silane containing an aromatic group as the terminal functional group and the second silane containing an amine group as the terminal functional group. Can be.
  • the first silane containing an aromatic group and the second silane containing an amine group may be similar to those described in the first embodiment.
  • the content of the inorganic nanofiller 25 surface-modified with silane in the internal discharge layer 20 is about 0.1 wt% to about 30 wt%, about 0.1 wt% to about 5 wt%, about 0.1 wt% to about 10 Wt%, about 0.1 wt% to about 20 wt%, about 0.1 wt% to about 30 wt%, about 5 wt% to about 10 wt%, about 5 wt% to about 20 wt%, about 5 wt% to about 30 Weight percent, about 10 weight percent to about 20 weight percent, about 10 weight percent to about 30 weight percent, or about 20 weight percent to about 30 weight percent.
  • the thickness of the internal discharge layer 20 may be 10 ⁇ m to 45 ⁇ m. However, the present invention is not limited thereto, and all thicknesses commonly applied in the art may be applied.
  • the thermal conductive layer 30 may be disposed on the internally discharged conductive layer 20.
  • the present invention is not limited thereto, and in this case, the internal discharge layer 20 may be omitted.
  • the thickness of the thermal conductive layer 30 may be 5 to 10 ⁇ m.
  • the thickness of the thermally conductive layer 30 may be 20 to 50 ⁇ m.
  • the thermal conductive layer 30 is composed of the composition described in the second embodiment, that is, the boron nitride 35 surface-modified with the first and second silanes described in the first embodiment, additionally with the third silane, the polymer precursor, And it can be prepared by coating a composition comprising the remainder of the solvent on the conductive wire 10, then drying and curing. In the coating process, after applying the composition on the conductive wire 10, the composition is uniformly coated on the conductive wire 10 by using a die (hollow cylindrical tool, dies). can do.
  • the thermal conductive layer 30 may include a polymer matrix cured by the polymer precursor in the curing process and boron nitride 35 surface-modified by multiple silanes dispersed in the polymer matrix.
  • the drying and curing steps may be performed at the same time. Specifically, rapid drying of the solvent and the curing may be simultaneously performed by applying strong heat of about 350 ° C to about 550 ° C. However, it is not limited thereto.
  • the polymer matrix is polyester, polyesterimide, polyesteramide, polyesteramideimide, (tri (2-hydroxyethyl) isocyanuate triacrylate) -polyesterimide, polyetherimide, polyamide, poly Amideimide, polyimide, polyurethane, polyvinyl formal, epoxy resin, phenolic resin, and combinations thereof may be included, but is not limited thereto.
  • the surface-modified boron nitride 35 has a surface modified by two or more silanes, and the first silane includes a first silane containing an aromatic group as a terminal functional group and a second containing an amine group or an epoxy group as a terminal functional group.
  • the chemical bond with the silane may be specifically surface modified by a siloxane bond.
  • the first silane containing an aromatic group and the second silane containing an amine group or an epoxy group may be similar to those described in the first embodiment.
  • the content of boron nitride surface-modified with multiple silanes in the thermally conductive layer 30 is about 0.1 wt% to about 60 wt%, about 0.1 wt% to about 30 wt%, about 0.1 wt% to about 5 wt% , About 0.1 wt% to about 10 wt%, about 0.1 wt% to about 20 wt%, about 0.1 wt% to about 30 wt%, about 5 wt% to about 10 wt%, about 5 wt% to about 20 wt% , About 5 wt% to about 30 wt%, about 10 wt% to about 20 wt%, about 10 wt% to about 30 wt%, or about 20 wt% to about 30 wt%, but is not limited thereto. .
  • the thickness of the thermal conductive layer 30 may be larger than the thickness of the boron nitride 35.
  • the boron nitride 35 may have a hexagonal mesh layer or a structure in which a plurality of mesh layers are stacked.
  • the boron nitride 35 may be a plate-shaped particle having one or two or more laminated plates, one of the upper and lower surfaces corresponding to the surface of the mesh layer of the boron nitride 35 being the conductive wire 10. It may be arranged to look at the surface of).
  • the angle ⁇ 1 of the plate-like surface of the boron nitride 35 with the surface of the conductive wire 10 is such that the plate-shaped surface of the boron nitride 35 is perpendicular to the surface of the conductive wire 10. It may be smaller than the angle ⁇ 2 with the waterline.
  • the boron nitride 35 may have an arrangement lying in the thermal conductive layer 30, so that the overlap between the boron nitrides 35 may be improved, thereby increasing thermal conductivity.
  • the plate-like surface of the boron nitride 35 may be disposed in parallel with the surface of the conductive wire 10.
  • the dispersibility of the boron nitride 35 may be reduced by the rapid thermal movement around the heat generated by the heat, but the boron nitride 35 surface-modified by multiple silane is As described above, since the aromatic group is retained on its surface, the polymer matrix having the aromatic group can be strongly interacted by ⁇ - ⁇ interaction, so that high dispersibility can be maintained even in this case.
  • the coil may then be heat treated, for example at a temperature of about 150 ° C. to 250 ° C.
  • the surfaces of the wire may be fused to each other to remove the air layer between the wires.
  • the polymer matrix in the thermal conductive layer 30 may be wound and fused to each other between adjacent wires.
  • the melting point of the polymer matrix may be selected to adjust the heat treatment temperature or to select a polymer constituting the polymer matrix to have a lower value than the heat treatment temperature.
  • 'PN' N- [3- (trimethoxysilyl) propyl] aniline
  • the NMP solution in which PAI was dispersed at 33wt% was molded in a Teflon mold, and then cured in a hot air oven at 240 ° C. for 240 minutes to obtain PAI pellets.
  • Table 1 below shows the thermal conductivity of boron nitride-PAI composite pellets or PAI pellets according to Experimental Examples 1 and Comparative Examples 1 to 5. At this time, the thermal conductivity was measured using a laser flash method.
  • FIG. 3a is a photograph of the fracture surface of the boron nitride-PAI complex according to Experimental Example 1
  • FIG. 3b is a photograph of the fracture surface of the boron nitride-PAI complex according to Comparative Example 2 .
  • the boron nitride-PAI composite containing the surface-modified boron nitride is a PAI resin with voids between boron nitrides as boron nitride is not completely dispersed. It can be seen that it is not filled by.
  • the boron nitride-PAI composite according to Experimental Example 1 surface-modified with a silane (DN) having an amine group as a terminal functional group and a silane (PN) having a phenyl group as a terminal functional group (FIG. 3A) has almost no porosity. It can be seen that.
  • boron nitride surface-modified with a silane (DN) having an amine group as a terminal functional group and a silane (PN) having a phenyl group as a terminal functional group is present in the PAI matrix. It can be seen that the degree of dispersion is better than the other cases.
  • YD-128 epoxy Kermo Chemical Co., Ltd.
  • Jeffoxy Hybrid Chemical Co., Ltd.
  • a polyoxyalkyleneamine-based curing agent a polyoxyalkyleneamine-based curing agent
  • the mixture was added at a concentration of% (25 parts by weight of surface-modified hexagonal boron nitride with respect to 100 parts by weight of the weight of YD-128 epoxy and zephamine) and mixed evenly.
  • the mixture was poured into a Teflon mold and cured in a hot air oven for 130 ° C. for 60 minutes to obtain a composite of boron nitride and epoxy surface-modified with PN and DN in pellet form.
  • a concentration of 20wt% (YD-) was added to a mixed solution of hexagonal boron nitride surface-modified with PN and YD-128 epoxy (Kukdo Chemical Co., Ltd.) and Jeffamine (Huntsman Co., Ltd.) in a ratio of 5: 3. 128 parts by weight of a surface modified hexagonal boron nitride) was added to 100 parts by weight of the epoxy and zephamine), and then molded in a Teflon mold. The molded mixture was cured in a hot air oven at 130 ° C. for 60 minutes to obtain a composite of boron nitride and epoxy surface-modified with PN in pellet form.
  • the boron nitride-epoxy complex according to Experimental Example 2 which is surface-modified with silane (DN) having an amine group as a terminal functional group and a silane (PN) having a phenyl group as a terminal functional group,
  • DN silane
  • PN silane
  • Figure 4a is a photograph of the fracture surface of the boron nitride-epoxy composite according to Experimental Example 2 with a scanning electron microscope
  • Figure 4b is a photograph of a fracture surface of the boron nitride-epoxy composite according to Comparative Example 7 with a scanning microscope .
  • the boron nitride-epoxy composite containing the surface-modified boron nitride (Comparative Example 7, FIG. 4B) has an epoxy resin with voids between the boron nitrides as boron nitride is not completely dispersed. It can be seen that it is not filled by.
  • the boron nitride-epoxy composite according to Experimental Example 2 surface-modified with a silane (DN) having an amine group as a terminal functional group and a silane (PN) having a phenyl group as a terminal functional group (FIG. 4A) has a fracture surface with little voids. It can be seen that.

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  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un nitrure de bore à surfaces modifiées multiples, une composition ayant des particules de ce dernier dispersées en son sein, et un câble revêtu de la composition. Le nitrure de bore à surfaces modifiées multiple est doté: de particules de nitrure de bore; d'un premier modificateur de surface se liant à la surface des particules de nitrure de bore et contenant un groupe aromatique à une extrémité; et d'un second modificateur de surface se liant à la surface des particules de nitrure de bore et contenant un groupe amine ou un groupe époxy à une extrémité.
PCT/KR2015/009910 2014-09-22 2015-09-22 Nitrure de bore modifié en surface, composition ayant des particules de celui-ci dispersées en son sein, et câble revêtu de la composition WO2016047988A1 (fr)

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KR20140126118 2014-09-22
KR10-2014-0126118 2014-09-22
KR10-2015-0130543 2015-09-15
KR1020150130543A KR102262025B1 (ko) 2014-09-22 2015-09-15 표면 개질된 질화붕소, 상기 입자가 분산된 조성물, 및 상기 조성물로 코팅된 와이어

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CN113337230A (zh) * 2021-05-11 2021-09-03 广东创辉鑫材科技股份有限公司 一种金属基板的高导热半固化胶膜及其制备方法
CN114956867A (zh) * 2022-05-19 2022-08-30 青岛理工大学 一种改性六方氮化硼-硅烷复合乳液及其制备方法和应用、混凝土的表面防护方法
CN115521736A (zh) * 2022-10-28 2022-12-27 江苏鸿佳电子科技有限公司 一种led封装用复合膜及其制备方法
CN115558243A (zh) * 2022-10-12 2023-01-03 富地润滑科技股份有限公司 摩擦改性的环氧树脂复合材料、其制备方法及摩擦结构
CN115928250A (zh) * 2022-12-12 2023-04-07 南京众山电池电子有限公司 一种聚酯纤维绝缘材料的制备方法和应用

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CN113337230A (zh) * 2021-05-11 2021-09-03 广东创辉鑫材科技股份有限公司 一种金属基板的高导热半固化胶膜及其制备方法
CN113337230B (zh) * 2021-05-11 2022-03-15 广东创辉鑫材科技股份有限公司 一种金属基板的高导热半固化胶膜及其制备方法
CN114956867A (zh) * 2022-05-19 2022-08-30 青岛理工大学 一种改性六方氮化硼-硅烷复合乳液及其制备方法和应用、混凝土的表面防护方法
CN114956867B (zh) * 2022-05-19 2023-03-03 青岛理工大学 一种改性六方氮化硼-硅烷复合乳液及其制备方法和应用、混凝土的表面防护方法
CN115558243A (zh) * 2022-10-12 2023-01-03 富地润滑科技股份有限公司 摩擦改性的环氧树脂复合材料、其制备方法及摩擦结构
CN115558243B (zh) * 2022-10-12 2024-05-28 富地润滑科技股份有限公司 摩擦改性的环氧树脂复合材料、其制备方法及摩擦结构
CN115521736A (zh) * 2022-10-28 2022-12-27 江苏鸿佳电子科技有限公司 一种led封装用复合膜及其制备方法
CN115521736B (zh) * 2022-10-28 2023-05-12 江苏鸿佳电子科技有限公司 一种led封装用复合膜及其制备方法
CN115928250A (zh) * 2022-12-12 2023-04-07 南京众山电池电子有限公司 一种聚酯纤维绝缘材料的制备方法和应用
CN115928250B (zh) * 2022-12-12 2024-05-28 南京众山电池电子有限公司 一种聚酯纤维绝缘材料的制备方法和应用

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