CN102876272A - Heat-conduction binding material and preparation method thereof - Google Patents
Heat-conduction binding material and preparation method thereof Download PDFInfo
- Publication number
- CN102876272A CN102876272A CN2012103658822A CN201210365882A CN102876272A CN 102876272 A CN102876272 A CN 102876272A CN 2012103658822 A CN2012103658822 A CN 2012103658822A CN 201210365882 A CN201210365882 A CN 201210365882A CN 102876272 A CN102876272 A CN 102876272A
- Authority
- CN
- China
- Prior art keywords
- parts
- heat conduction
- matrix material
- component
- inorganic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a heat-conduction binding material. The heat-conduction binding material is formed by mixing components A and components B, wherein the components A include 100 parts of epoxy resin, 20-30 parts of reactive diluent, 30-50 parts of modified inorganic heat-conduction materials and 10-15 parts of organic solvent according to mass ratio and the modified inorganic heat-conduction materials are formed by coupling agents adsorbing on surfaces of inorganic heat-conduction particles. The components B include curing agents and organic solvents. The coupling agents are adsorbed on the inorganic heat-conduction particles to form the modified inorganic heat-conduction materials, so that compatibility of the inorganic particles in the organic resin can be improved, boundary defects and boundary stress between inorganic materials and organic materials after curing are reduced, organic layers among the inorganic heat-conduction particles can be reserved on the condition of adding a great quantity of modified inorganic heat-conduction materials, binding force of the heat-conduction binding material is improved, and accordingly, the heat-conduction binding material is better in mechanical performance. The invention further provides a preparation method of the heat-conduction binding material.
Description
Technical field
The present invention relates to a kind of heat conduction matrix material and preparation method thereof.
Background technology
Along with microelectronics and unicircuit develop rapidly, electron device constantly advances towards high frequency, high assembled density and small size direction, especially recent years is urgent to the demand of high-power electronic product, heat radiation has become the key factor that affects electronic reliability and work-ing life, heat dissipation problem has been electronic component progress of miniaturization significant obstacle, and heat transmission and heat dissipation performance have been the important performance assessment criteria of package level height.At present, the heat conduction matrix material has become one of indispensable means that solve heat dissipation problem, and particularly in the Electronic Packaging field, insulated type epoxy group(ing) heat-conducting glue matrix material is widely adopted, is paid much attention to.
The thermal conductivity great majority of traditional heat conduction matrix material all below 2.0W/ (m.K), can not satisfy actual high-power, height integrated electronic product development need.
Generally can increase by adding inorganic heat conduction particle the thermal conductivity of heat conduction matrix material.When the addition of heat conduction matrix material is less, exist inorganic heat conduction particle to form to each other contact and interactional state, both failed to form thermal conducting path, the thermal conductivity of heat conduction matrix material improves not quite.Along with the increase of the addition of inorganic heat conduction particle, form contact between inorganic heat conduction particle or interact, will form similar netted or chain-like structure form in the heat conduction matrix material, heat conductivility improves very fast thermal resistance and will reduce, and thermal conductivity will increase.Be increased to a certain degree but work as inorganic heat conduction particle, the heat conduction matrix material can be because inorganic heat conduction particle too much make the organic layer between inorganic heat conduction particle be torn.And the mechanical mechanics property of the heat conduction matrix material under this state can not meet the demands far away.
Summary of the invention
Based on this, be necessary to provide heat conduction matrix material of the higher and better mechanical property of a kind of thermal conductivity and preparation method thereof.
A kind of heat conduction matrix material mixes after fixing by component A and B component and forms;
Described component A comprises 100 parts Resins, epoxy, 20 parts ~ 30 parts reactive thinner, 30 parts ~ 50 parts modified inorganic thermally conductive material and 10 parts ~ 15 parts organic solvent according to mass ratio; Wherein, described modified inorganic thermally conductive material is that coupling agent is adsorbed on the surface formation of inorganic heat conduction particle;
Described B component comprises solidifying agent and described organic solvent.
In one embodiment, described Resins, epoxy is at least a in glycidyl ether based epoxy resin and the alicyclic based epoxy resin.
In one embodiment, described reactive thinner is at least a in epoxy group(ing) hexanediol diglycidyl ether, epoxy group(ing) diglycidyl ether of ethylene glycol, benzyl glycidyl ether and the butylglycidyl ether.
In one embodiment, described inorganic heat conduction particle comprises Al
2O
3, AlN, Si
3N
4With the conductive graphite powder.
In one embodiment, described Al
2O
3Particle diameter be 0.5 μ m ~ 6 μ m, the particle diameter of described AlN is 1 μ m ~ 5 μ m, described Si
3N
4Particle diameter be 0.5 μ m ~ 4 μ m, the particle diameter of described conductive graphite powder is 10 μ m ~ 15 μ m.
In one embodiment, described coupling agent is at least a in γ-(methacryloxypropyl) propyl trimethoxy silicane, γ-(2,3) epoxy (propoxy-) propyl trimethoxy silicane, γ-aminopropyl triethoxysilane, tetra isopropyl two (dioctyl phosphite) titanic acid ester, vinyl three (b-methoxy ethoxy) silane and the vinyltriethoxysilane.
In one embodiment, described B component comprises 30 parts ~ 45 parts described solidifying agent and 10 parts ~ 15 parts described organic solvent according to mass ratio;
Described solidifying agent is Versamid, modified multicomponent amine or phthalic anhydride.
In one embodiment, described component A also comprises 4 parts ~ 6 parts toughner.
In one embodiment, described component A also comprises at least a in 0.6 part ~ 1.5 parts curing catalyst, UV light absorber, anti-xanthochromia agent and the antioxidant.
A kind of preparation method of heat conduction matrix material comprises the steps:
According to massfraction 0.3 part ~ 1.5 parts coupling agent is dissolved in and is mixed with the alcohol solution that concentration is 3mg/mL ~ 15mg/mL in the alcohol-water mixture, according to massfraction 30 parts ~ 50 parts inorganic heat conduction particle is dispersed in water and obtains the suspension that concentration is 150mg/mL ~ 300mg/mL, take out after with described alcohol solution and described suspension mixing 1.5h ~ 3h dry at 50 ℃ ~ 70 ℃, described coupling agent is adsorbed on inorganic heat conduction particle surface, obtains the modified inorganic thermally conductive material;
According to massfraction under 55 ℃ ~ 65 ℃ with 100 parts Resins, epoxy, 20 parts ~ 30 parts reactive thinner and 30 parts ~ 50 parts described modified inorganic thermally conductive material mixing, obtain intermediate product, the organic solvent that then at room temperature adds 10 parts ~ 15 parts to described intermediate product, grind behind the mixing and carry out the vacuum outgas bubble and process, obtain component A;
At room temperature 30 parts ~ 45 parts solidifying agent is distributed to according to massfraction in 10 parts ~ 15 parts the described organic solvent, obtains B component; And
Described component A and described B component mixing after fixing are formed described heat conduction matrix material.
This heat conduction matrix material is adsorbed on the modified inorganic thermally conductive material that inorganic heat conduction particle forms by coupling agent, can strengthen the consistency of inorganic particle in organic resin, can reduce and solidify boundary defect and the interfacial stress that exists between rear inorganics and the organism, thereby can in the interpolation modified inorganic thermally conductive material of more amount, be retained preferably by the organic layer between inorganic heat conduction particle, strengthened the bonding force of heat conduction matrix material, thus so that the better mechanical property of heat conduction matrix material.With respect to traditional heat conduction matrix material, higher, the better mechanical property of the thermal conductivity of this heat conduction matrix material.
Description of drawings
Fig. 1 is preparation method's the schema of the heat conduction matrix material of an embodiment.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement much to be different from alternate manner described here, and those skilled in the art can do similar improvement in the situation of intension of the present invention, so the present invention is not subjected to the restriction of following public implementation.
The heat conduction matrix material of one embodiment mixes after fixing by component A and B component and forms.
Component A comprises 100 parts Resins, epoxy, 20 parts ~ 30 parts reactive thinner, 30 parts ~ 50 parts modified inorganic thermally conductive material and 10 parts ~ 15 parts organic solvent according to mass ratio.
Resins, epoxy can be in glycidyl ether based epoxy resin and the alicyclic based epoxy resin at least a.
Concrete, what Resins, epoxy can be among glycidyl ether based epoxy resin E44, glycidyl ether based epoxy resin E51, alicyclic based epoxy resin CY179 and the alicyclic based epoxy resin CY184 is at least a.
Reactive thinner can be in epoxy group(ing) hexanediol diglycidyl ether, epoxy group(ing) diglycidyl ether of ethylene glycol, benzyl glycidyl ether and the butylglycidyl ether at least a.
The modified inorganic thermally conductive material is that coupling agent is adsorbed on the surface formation of inorganic heat conduction particle.The modified inorganic thermally conductive material surface that coupling agent is adsorbed on inorganic heat conduction particle formation has chemically reactive functional group, thereby can strengthen the consistency of inorganic particle in organic resin, can reduce and solidify boundary defect and the interfacial stress that exists between rear inorganics and the organism.
Inorganic heat conduction particle comprises Al
2O
3, AlN, Si
3N
4With conductive graphite powder etc.
Al
2O
3Thermal conductivity be 35W/ (mK), a-Al
2O
3Monocrystalline has the advantages such as thermal conductivity height, dielectric strength be large.
The thermal conductivity of β-Si3N4 is 80W/ (mK), represented good application prospect in fields such as microwave permeable material and microelectronic packaging material, the factor that affects its thermal conductivity is mainly the anisotropy of defective, grain-size and microtexture in Grain-Boundary Phase phase and content thereof, the lattice etc.
S
i3N
4The increase of content in the heat conduction matrix material can cause forming the heat conduction network in the heat conduction matrix material, thereby increases the thermal conductivity of heat conduction matrix material.
The thermal conductivity of the conductive graphite powder of monocrystalline is 490W/ (mK), and the thermal conductivity of the conductive graphite powder of polycrystalline is about 60/ (mK).
Adopt Al
2O
3, AlN, Si
3N
4Improve bonding force and the dispersiveness of heat conduction matrix material with four kinds of different inorganic heat conduction particles of conductive graphite powder, thereby the thermal conductivity of heat conduction matrix material improves further.
In the present embodiment, Al
2O
3Particle diameter be 0.5 μ m ~ 6 μ m, the particle diameter of AlN is 1 μ m ~ 5 μ m, S
i3N
4Particle diameter be 0.5 μ m ~ 4 μ m, the particle diameter of conductive graphite powder is 10 μ m ~ 15 μ m.
Can play complementary action between the inorganic heat conduction particle of different-grain diameter and shape, strengthen the addition of inorganic heat conduction particle in the heat conduction matrix material, the heat conductivility of Effective Raise heat conduction matrix material.
Coupling agent can be in γ-(methacryloxypropyl) propyl trimethoxy silicane (KH570), γ-(2,3) epoxy (propoxy-) propyl trimethoxy silicane (KH560), γ-aminopropyl triethoxysilane (KH550), tetra isopropyl two (dioctyl phosphite) titanic acid ester (NDZ-401), vinyl three (b-methoxy ethoxy) silane (A172) and the vinyltriethoxysilane (A151) at least a.
Organic solvent can be ethanol, acetone, dimethylbenzene, toluene or benzene.
In the present embodiment, component A can also comprise 4 parts ~ 6 parts toughner.
Softening agent can be dibutyl phthalate, dioctyl phthalate (DOP), diheptyl phthalate (DHP), Di Iso Decyl Phthalate (DIDP) or dimixo-octyl phthalate.
In the present embodiment, component A can also comprise at least a in 0.6 part ~ 1.5 parts curing catalyst, UV light absorber, anti-xanthochromia agent and the antioxidant.
Curing catalyst can be 2,4,6-three (dimethylamino methyl) phenol (DMP-30).
UV light absorber can be 2-(2H-benzotriazole-2-yl) p-cresol.
Antioxidant can be tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester.
Anti-xanthochromia agent can be composite anti-yellowing change agent V76-P or anti-yellowing change agent V78-P.
B component comprises 30 parts ~ 45 parts solidifying agent and 10 parts ~ 15 parts above-mentioned organic solvent according to mass ratio.
Solidifying agent can be Versamid, modified multicomponent amine or phthalic anhydride.
Concrete, solidifying agent can be polyamide 6 00 solidifying agent, polyamide 6 50 solidifying agent, modified multicomponent amine T31 solidifying agent, methyl tetrahydro phthalic anhydride or methyl hexahydrophthalic anhydride.
This heat conduction matrix material mixes component A and B component when in use, gets final product.
This heat conduction matrix material is adsorbed on the modified inorganic thermally conductive material that inorganic heat conduction particle forms by coupling agent, can strengthen the consistency of inorganic particle in organic resin, can reduce and solidify boundary defect and the interfacial stress that exists between rear inorganics and the organism, thereby can in the interpolation modified inorganic thermally conductive material of more amount, be retained preferably by the organic layer between inorganic heat conduction particle, strengthened the bonding force of heat conduction matrix material, thus so that the better mechanical property of heat conduction matrix material.With respect to traditional heat conduction matrix material, higher, the better mechanical property of the thermal conductivity of this heat conduction matrix material.
The preparation method of above-mentioned heat conduction matrix material as shown in Figure 1 comprises the steps:
S10, according to massfraction 0.3 part ~ 1.5 parts coupling agent is dissolved in and is mixed with the alcohol solution that concentration is 3mg/mL ~ 15mg/mL in the alcohol-water mixture, according to massfraction 30 parts ~ 50 parts inorganic heat conduction particle is dispersed in water and obtains the suspension that concentration is 150mg/mL ~ 300mg/mL, take out after with described alcohol solution and described suspension mixing 1.5h ~ 3h dry at 50 ℃ ~ 70 ℃, described coupling agent is adsorbed on inorganic heat conduction particle surface, obtains the modified inorganic thermally conductive material.
Alcohol-water mixture can be the mixed solution of 95:5 ~ 90:10 with water volume ratio for alcohol.
Drying can be lyophilize or spraying drying.
S20, the modified inorganic thermally conductive material mixing that under 55 ℃ ~ 65 ℃, the S10 of 100 parts Resins, epoxy, 20 parts ~ 30 parts reactive thinner and 30 parts ~ 50 parts is obtained according to massfraction, obtain intermediate product, the organic solvent that then at room temperature adds 10 parts ~ 15 parts to described intermediate product, grind behind the mixing and carry out the vacuum outgas bubble and process, obtain component A.
Generally can select first under 55 ℃ ~ 65 ℃ the Resins, epoxy mixing with 100 parts, then keeping temperature is 55 ℃ ~ 65 ℃ reactive thinner mixings that add 20 parts ~ 30 parts, add at last 30 parts ~ 50 parts modified inorganic thermally conductive material mixing, thereby obtain intermediate product.
The mode of mixing can adopt stirring, and is concrete, can directly stir, or use stirrer to stir.
Obtain in the operation of intermediate product, also can add simultaneously 4 parts ~ 6 parts toughner, 0.6 part ~ 1.5 parts curing catalyst, UV light absorber, anti-xanthochromia agent or antioxidant, mixing gets final product behind the interpolation mentioned component.
The time that the vacuum outgas bubble is processed can be 0.5h ~ 1h, and this operates under the 0.1Mpa normal atmosphere and carries out.
S30, at room temperature 30 parts ~ 45 parts solidifying agent is distributed to according to massfraction in 10 parts ~ 15 parts the described organic solvent, obtains B component.
The B component that S40, the component A that S20 is obtained and S30 obtain is mixed after fixing and is formed the heat conduction matrix material.
Below be specific embodiment, all umbers that wherein occur are massfraction.The model that adopts Beijing hat test to test Instr Ltd.'s production is the high resistance Micrometer of current of GEST-121, the resistivity of the heat-conducting glue matrix material of test patent of the present invention; The model that adopts Xiangtan City instrument company limited to produce is the thermal conductivity that the Determination of conductive coefficients instrument of DRP-II is measured the heat-conducting glue matrix material of patent of the present invention.
Embodiment 1
1.5 parts A172 are mixed with alcohol solution, and (volume of alcohol-water mixture is 100mL, volume ratio of alcohol to water is 90/10), 300rpm dispersed with stirring half hour, it is the suspension liquid of 200mg/mL that 50 parts inorganic heat conduction particle is dispersed in water the concentration that obtains, under 60 ℃, alcohol solution and suspension liquid are mixed, take out and spraying drying behind the 2h, A172 is adsorbed on inorganic heat conduction particle surface, obtains the modified inorganic thermally conductive material.In the present embodiment, inorganic heat conduction particle is 4 parts Al
2O
3, 21 parts AlN, 18 parts Si
3N
4The mixture that forms with 7 parts conductive graphite powder.
First 60 parts E51 resin is heated to 60 ℃, adds 40 parts CY179 resin under the stirring action, mix and blend 0.5h.The epoxy group(ing) hexanediol diglycidyl ether that adds afterwards 25 parts, restir 0.5h, the modification heat conduction ultrafine particle of 50 parts of rear addings stirs under the 1500rpm rotating speed, restir 0.5h, then temperature is dropped to room temperature by 60 ℃, add 8 parts ethanol, 5 parts dibutyl phthalate, 0.2 part DMP-30,0.2 part V76-P and 0.2 part tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, grind 1h behind the continuously stirring 0.5h, 0.1Mpa under the normal atmosphere, the vacuum outgas bubble is processed 1h, obtains component A.
5 parts 650 solidifying agent, 10 parts T31 solidifying agent, 30 parts methyl tetrahydro phthalic anhydride and 12 parts ethanol are joined in the stirring dispersion machine, under the 1500rpm rotating speed, stir 1h, obtain B component.
The thermal conductivity of heat conduction matrix material and resistivity measurement: after component A and B component mixed stirring, 0.1Mpa under the normal atmosphere, the vacuum outgas bubble is processed 10min, after applying, being heating and curing, the thermal conductivity that records the heat conduction matrix material is 4.2W/ (mK), and resistivity is 6.17 * 10
15Ω cm.
Embodiment 2
0.3 part NDZ-401 is mixed with alcohol solution, and (volume of alcohol-water mixture is 100mL, volume ratio of alcohol to water is 90/10), 300rpm dispersed with stirring half hour, it is the suspension liquid of 150mg/mL that 48 parts inorganic heat conduction particle is dispersed in water the concentration that obtains, under 50 ℃, alcohol solution and suspension liquid are mixed, take out and lyophilize behind the 2h, NDZ-401 is adsorbed on inorganic heat conduction particle surface, obtains the modified inorganic thermally conductive material.In the present embodiment, inorganic heat conduction particle is 3 parts Al
2O
3, 22 parts AlN, 16 parts Si
3N
4The mixture that forms with 7 parts conductive graphite powder.
First 65 parts E51 resin is heated to 55 ℃, adds 35 parts CY179 resin under the stirring action, mix and blend 0.5h.The epoxy group(ing) hexanediol diglycidyl ether that adds afterwards 25 parts, restir 0.5h, the modification heat conduction ultrafine particle of 48 parts of rear addings stirs under the 1500rpm rotating speed, restir 0.5h, then temperature is dropped to room temperature by 60 ℃, add 8 parts ethanol, 5 parts dibutyl phthalate, 0.2 part DMP-30,0.3 part V78-P and 0.3 part tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, grind 1h behind the continuously stirring 0.5h, 0.1Mpa under the normal atmosphere, the vacuum outgas bubble is processed 0.5h, obtains component A.
10 parts 600 solidifying agent, 5 parts T31 solidifying agent, 30 parts methyl tetrahydro phthalic anhydride and 12 parts ethanol are joined in the stirring dispersion machine, under the 1500rpm rotating speed, stir 1h, obtain B component.
The thermal conductivity of heat conduction matrix material and resistivity measurement: after component A and B component mixed stirring, 0.1Mpa under the normal atmosphere, the vacuum outgas bubble is processed 5min, after applying, being heating and curing, the thermal conductivity that records the heat conduction matrix material is 4.0W/ (mK), and resistivity is 6.28 * 10
15Ω .cm.
Embodiment 3
1 part KH560 is mixed with alcohol solution, and (volume of alcohol-water mixture is 100mL, volume ratio of alcohol to water is 90/10), 300rpm dispersed with stirring half hour, it is the suspension liquid of 200mg/mL that 45 parts inorganic heat conduction particle is dispersed in water the concentration that obtains, under 55 ℃ alcohol solution and suspension liquid are mixed, take out and spraying drying behind the 2h, KH560 is adsorbed on inorganic heat conduction particle surface, obtains the modified inorganic thermally conductive material.In the present embodiment, inorganic heat conduction particle is 2 parts Al
2O
3, 24 parts AlN, 13 parts Si
3N
4The mixture that forms with 6 parts conductive graphite powder.
First 70 parts E51 resin is heated to 65 ℃, adds 30 parts CY179 resin under the stirring action, mix and blend 0.5h.The epoxy group(ing) hexanediol diglycidyl ether that adds afterwards 25 parts, restir 0.5h, the modification heat conduction ultrafine particle of 45 parts of rear addings stirs under the 1500rpm rotating speed, restir 0.5h, then reduce the temperature to room temperature, add 8 parts ethanol, 5 parts DMP-30,0.3 part the V78-P of 0.2 part of dibutyl phthalate and 0.4 part tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, grind 1h behind the continuously stirring 0.5h, 0.1Mpa under the normal atmosphere, the vacuum outgas bubble is processed 1h, obtains component A.
13 parts 650 solidifying agent, 8 parts T31 solidifying agent, 24 parts methyl tetrahydro phthalic anhydride and 13 parts ethanol are joined in the stirring dispersion machine, under the 1500rpm rotating speed, stir 1h, obtain B component.
The thermal conductivity of heat conduction matrix material and resistivity measurement: after component A and B component mixed stirring, 0.1Mpa under the normal atmosphere, the vacuum outgas bubble is processed 10min, after applying, being heating and curing, the thermal conductivity that records the heat conduction matrix material is 3.9W/ (m.K), and resistivity is 5.84 * 10
15Ω .cm.
Embodiment 4
1.2 parts KH550 are mixed with alcohol solution, and (volume of alcohol-water mixture is 100mL, volume ratio of alcohol to water is 90/10), 300rpm dispersed with stirring half hour, it is the suspension liquid of 200mg/mL that 46 parts inorganic heat conduction particle is dispersed in water the concentration that obtains, under 65 ℃ alcohol solution and suspension liquid are mixed, 1.5h rear the taking-up and spraying drying, KH550 is adsorbed on inorganic heat conduction particle surface, obtains the modified inorganic thermally conductive material.In the present embodiment, inorganic heat conduction particle is 4 parts Al
2O
3, 16 parts AlN, 20 parts S
i3N
4The mixture that forms with 6 parts conductive graphite powder.
First 75 parts E51 resin is heated to 60 ℃, adds 25 parts CY179 resin under the stirring action, mix and blend 0.5h.The epoxy group(ing) hexanediol diglycidyl ether that adds afterwards 25 parts, restir 0.5h, the modification heat conduction ultrafine particle of 46 parts of rear addings stirs under the 1500rpm rotating speed, restir 0.5h, then reduce the temperature to room temperature, add 8 parts ethanol, 5 parts dibutyl phthalate, 0.2 part DMP-30,0.3 part V76-P, 0.5 part antioxidant and 0.1 part 2-(2H-benzotriazole-2-yl) p-cresol, grind 1h behind the continuously stirring 0.5h, 0.1Mpa under the normal atmosphere, the vacuum outgas bubble is processed 1h, obtains component A.
10 parts 600 solidifying agent, 5 parts T31 solidifying agent, 20 parts methyl tetrahydro phthalic anhydride and 12 parts ethanol are joined in the stirring dispersion machine, under the 1500rpm rotating speed, stir 1h, obtain B component.
The thermal conductivity of heat conduction matrix material and resistivity measurement: after component A and B component mixed stirring, 0.1Mpa under the normal atmosphere, the vacuum outgas bubble is processed 10min, after applying, being heating and curing, the thermal conductivity that records the heat conduction matrix material is 3.4W/ (m.K), and resistivity is 6.05 * 10
15Ω .cm.
Embodiment 5
0.8 part NDZ-401 is mixed with alcohol solution, and (volume of alcohol-water mixture is 100mL, volume ratio of alcohol to water is 90/10), 300rpm dispersed with stirring half hour, it is the suspension liquid of 250mg/mL that 40 parts inorganic heat conduction particle is dispersed in water the concentration that obtains, under 70 ℃ alcohol solution and suspension liquid are mixed, 2.5h rear the taking-up and spraying drying, NDZ-401 is adsorbed on inorganic heat conduction particle surface, obtains the modified inorganic thermally conductive material.In the present embodiment, inorganic heat conduction particle is 4 parts Al
2O
3, 19 parts AlN, 12 parts Si
3N
4The mixture that forms with 5 parts conductive graphite powder.
First 70 parts E51 resin is heated to 60 ℃, adds 30 parts CY184 resin under the stirring action, mix and blend 0.5h.The epoxy group(ing) hexanediol diglycidyl ether that adds afterwards 25 parts, restir 0.5h, the modification heat conduction ultrafine particle of 40 parts of rear addings stirs under the 1500rpm rotating speed, restir 0.5h, then reduce the temperature to room temperature, add 8 parts ethanol, 5 parts dibutyl phthalate, 0.2 part DMP-30,0.3 part V76-P and 0.4 part tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, grind 1h behind the continuously stirring 0.5h, 0.1Mpa under the normal atmosphere, the vacuum outgas bubble is processed 1h, obtains component A.
14 parts 650 solidifying agent, 8 parts T31 solidifying agent, 23 parts methyl tetrahydro phthalic anhydride and 12 parts ethanol are joined in the stirring dispersion machine, under the 1500rpm rotating speed, stir 1h, obtain B component.
The thermal conductivity of heat conduction matrix material and resistivity measurement: after component A and B component mixed stirring, 0.1Mpa under the normal atmosphere, the vacuum outgas bubble is processed 10min, after applying, being heating and curing, the thermal conductivity that records the heat conduction matrix material is 3.3W/ (m.K), and resistivity is 5.76 * 10
15Ω .cm.
Embodiment 6
1 part KH560 is mixed with alcohol solution, and (volume of alcohol-water mixture is 100mL, volume ratio of alcohol to water is 90/10), 300rpm dispersed with stirring half hour, it is the suspension liquid of 200mg/mL that 45 parts inorganic heat conduction particle is dispersed in water the concentration that obtains, under 65 ℃ alcohol solution and suspension liquid are mixed, 1.5h rear the taking-up and spraying drying, KH560 is adsorbed on inorganic heat conduction particle surface, obtains the modified inorganic thermally conductive material.In the present embodiment, inorganic heat conduction particle is 4 parts Al
2O
3, 16 parts AlN, 20 parts Si
3N
4The mixture that forms with 5 parts conductive graphite powder.
First 60 parts E51 resin is heated to 60 ℃, adds 40 parts E44 resin under the stirring action, mix and blend 0.5h.The epoxy group(ing) hexanediol diglycidyl ether that adds afterwards 20 parts, restir 0.5h, the modification heat conduction ultrafine particle of 45 parts of rear addings stirs under the 1500rpm rotating speed, restir 0.5h, then reduce the temperature to room temperature, the ethanol that adds 8 parts, 5 parts dibutyl phthalate, 0.3 the DMP-30 of part, 0.2 the V76-P of part, 0.5 the tricresyl phosphite (2 of part, the 4-di-tert-butyl-phenyl) 2-(2H-benzotriazole-2-yl) p-cresol of ester and 0.1 part, grind 1h behind the continuously stirring 0.5h, 0.1Mpa under the normal atmosphere, the vacuum outgas bubble is processed 1h, obtains component A.
12 parts 650 solidifying agent, 10 parts T31 solidifying agent, 16 parts methyl tetrahydro phthalic anhydride and 13 parts ethanol are joined in the stirring dispersion machine, under the 1500rpm rotating speed, stir 1h, obtain B component.
The thermal conductivity of heat conduction matrix material and resistivity measurement: after component A and B component mixed stirring, 0.1Mpa under the normal atmosphere, the vacuum outgas bubble is processed 10min, after applying, being heating and curing, the thermal conductivity that records the heat conduction matrix material is 3.4W/ (m.K), and resistivity is 6.16 * 10
15Ω .cm.
Embodiment 7
1 part KH570 is mixed with alcohol solution, and (volume of alcohol-water mixture is 100mL, volume ratio of alcohol to water is 90/10), 300rpm dispersed with stirring half hour, it is the suspension liquid of 250mg/mL that 48 parts inorganic heat conduction particle is dispersed in water the concentration that obtains, under 60 ℃ alcohol solution and suspension liquid are mixed, 2.5h rear the taking-up and lyophilize, KH570 is adsorbed on inorganic heat conduction particle surface, obtains the modified inorganic thermally conductive material.In the present embodiment, inorganic heat conduction particle is 4 parts Al
2O
3, 15 parts AlN, 24 parts Si
3N
4The mixture that forms with 5 parts conductive graphite powder.
First 80 parts E51 resin is heated to 60 ℃, adds 20 parts CY179 resin under the stirring action, mix and blend 0.5h.The epoxy group(ing) hexanediol diglycidyl ether that adds afterwards 20 parts, restir 0.5h, the modification heat conduction ultrafine particle of 48 parts of rear addings stirs under the 1500rpm rotating speed, restir 0.5h, then reduce the temperature to room temperature, the ethanol that adds 8 parts, 5 parts dibutyl phthalate, 0.2 the DMP-30 of part, 0.3 the V76-P of part, 0.4 the tricresyl phosphite (2 of part, the 4-di-tert-butyl-phenyl) 2-(2H-benzotriazole-2-yl) p-cresol of ester and 0.1 part, grind 1h behind the continuously stirring 0.5h, 0.1Mpa under the normal atmosphere, the vacuum outgas bubble is processed 1h, obtains component A.
12 parts 650 solidifying agent, 10 parts T31 solidifying agent, 16 parts methyl tetrahydro phthalic anhydride and 12 parts ethanol are joined in the stirring dispersion machine, under the 1500rpm rotating speed, stir 1h, obtain B component.
The thermal conductivity of heat conduction matrix material and resistivity measurement: after component A and B component mixed stirring, 0.1Mpa under the normal atmosphere, the vacuum outgas bubble is processed 10min, after applying, being heating and curing, the thermal conductivity that records the heat conduction matrix material is 3.6W/ (m.K), and resistivity is 6.37 * 10
15Ω .cm.
Embodiment 8
1 part KH550 is mixed with alcohol solution, and (volume of alcohol-water mixture is 100mL, volume ratio of alcohol to water is 90/10), 300rpm dispersed with stirring half hour, it is the suspension liquid of 250mg/mL that 35 parts inorganic heat conduction particle is dispersed in water the concentration that obtains, under 60 ℃ alcohol solution and suspension liquid are mixed, 2.5h rear the taking-up and spraying drying, KH550 is adsorbed on inorganic heat conduction particle surface, obtains the modified inorganic thermally conductive material.In the present embodiment, inorganic heat conduction particle is 3 parts Al
2O
3, 13 parts AlN, 14 parts Si
3N
4The mixture that forms with 5 parts conductive graphite powder.
First 100 parts E51 resin is heated to 60 ℃, the epoxy group(ing) hexanediol diglycidyl ether that adds afterwards 20 parts, restir 0.5h, the modification heat conduction ultrafine particle of 35 parts of rear addings stirs under the 1500rpm rotating speed, restir 0.5h, then reduce the temperature to room temperature, the ethanol that adds 8 parts, 5 parts dibutyl phthalate, 0.3 the DMP-30 of part, 0.4 the V78-P of part, 0.5 the tricresyl phosphite (2 of part, the 4-di-tert-butyl-phenyl) 2-(2H-benzotriazole-2-yl) p-cresol of ester and 0.2 part, grind 1h behind the continuously stirring 0.5h, 0.1Mpa under the normal atmosphere, the vacuum outgas bubble is processed 1h, obtains component A.
25 parts 650 solidifying agent, 10 parts T31 solidifying agent and 12 parts ethanol are joined in the stirring dispersion machine, under the 1500rpm rotating speed, stir 1h, obtain B component.
The thermal conductivity of heat conduction matrix material and resistivity measurement: after component A and B component mixed stirring, 0.1Mpa under the normal atmosphere, the vacuum outgas bubble is processed 10min, after applying, being heating and curing, the thermal conductivity that records the heat conduction matrix material is 2.4W/ (mK), and resistivity is 6.43 * 10
15Ω .cm.
Embodiment 9
1 part A151 is mixed with alcohol solution, and (volume of alcohol-water mixture is 100mL, volume ratio of alcohol to water is 90/10), 300rpm dispersed with stirring half hour, it is the suspension liquid of 300mg/mL that 46 parts inorganic heat conduction particle is dispersed in water the concentration that obtains, under 60 ℃ alcohol solution and suspension liquid are mixed, 2.5h rear the taking-up and spraying drying, A151 is adsorbed on inorganic heat conduction particle surface, obtains the modified inorganic thermally conductive material.In the present embodiment, inorganic heat conduction particle is 2 parts Al
2O
3, 12 parts AlN, 12 parts Si
3N
4The mixture that forms with 4 parts conductive graphite powder.
First 50 parts E51 resin is heated to 60 ℃, adds 50 parts E44 resin under the stirring action, mix and blend 0.5h.The epoxy group(ing) hexanediol diglycidyl ether that adds afterwards 20 parts, restir 0.5h, the modification heat conduction ultrafine particle of 30 parts of rear addings stirs under the 1500rpm rotating speed, restir 0.5h, then reduce the temperature to room temperature, the ethanol that adds 8 parts, 5 parts dibutyl phthalate, 0.3 the DMP-30 of part, 0.4 the V76-P of part, 0.6 the tricresyl phosphite (2 of part, the 4-di-tert-butyl-phenyl) 2-(2H-benzotriazole-2-yl) p-cresol of ester and 0.2 part, grind 1h behind the continuously stirring 0.5h, 0.1Mpa under the normal atmosphere, the vacuum outgas bubble is processed 1h, obtains component A.
20 parts 650 solidifying agent, 10 parts T31 solidifying agent and 12 parts ethanol are joined in the stirring dispersion machine, under the 1500rpm rotating speed, stir 1h, obtain B component.
The thermal conductivity of heat conduction matrix material and resistivity measurement: after component A and B component mixed stirring, 0.1Mpa under the normal atmosphere, the vacuum outgas bubble is processed 10min, after applying, being heating and curing, the thermal conductivity that records the heat conduction matrix material is 2.1W/ (mK), and resistivity is 6.56 * 10
15Ω cm.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a heat conduction matrix material mixes after fixing by component A and B component and forms, and it is characterized in that;
Described component A comprises 100 parts Resins, epoxy, 20 parts ~ 30 parts reactive thinner, 30 parts ~ 50 parts modified inorganic thermally conductive material and 10 parts ~ 15 parts organic solvent according to mass ratio; Wherein, described modified inorganic thermally conductive material is that coupling agent is adsorbed on the surface formation of inorganic heat conduction particle;
Described B component comprises solidifying agent and described organic solvent.
2. heat conduction matrix material according to claim 1 is characterized in that, described Resins, epoxy is at least a in glycidyl ether based epoxy resin and the alicyclic based epoxy resin.
3. heat conduction matrix material according to claim 1 is characterized in that, described reactive thinner is at least a in epoxy group(ing) hexanediol diglycidyl ether, epoxy group(ing) diglycidyl ether of ethylene glycol, benzyl glycidyl ether and the butylglycidyl ether.
4. heat conduction matrix material according to claim 1 is characterized in that, described inorganic heat conduction particle comprises Al
2O
3, AlN, Si
3N
4With the conductive graphite powder.
5. heat conduction matrix material according to claim 4 is characterized in that, described Al
2O
3Particle diameter be 0.5 μ m ~ 6 μ m, the particle diameter of described AlN is 1 μ m ~ 5 μ m, described Si
3N
4Particle diameter be 0.5 μ m ~ 4 μ m, the particle diameter of described conductive graphite powder is 10 μ m ~ 15 μ m.
6. heat conduction matrix material according to claim 1, it is characterized in that, described coupling agent is at least a in γ-(methacryloxypropyl) propyl trimethoxy silicane, γ-(2,3) epoxy (propoxy-) propyl trimethoxy silicane, γ-aminopropyl triethoxysilane, tetra isopropyl two (dioctyl phosphite) titanic acid ester, vinyl three (b-methoxy ethoxy) silane and the vinyltriethoxysilane.
7. heat conduction matrix material according to claim 1 is characterized in that, described B component comprises 30 parts ~ 45 parts described solidifying agent and 10 parts ~ 15 parts described organic solvent according to mass ratio;
Described solidifying agent is Versamid, modified multicomponent amine or phthalic anhydride.
8. heat conduction matrix material according to claim 1 is characterized in that, described component A also comprises 4 parts ~ 6 parts toughner.
9. heat conduction matrix material according to claim 1 is characterized in that, described component A also comprises at least a in 0.6 part ~ 1.5 parts curing catalyst, UV light absorber, anti-xanthochromia agent and the antioxidant.
10. the preparation method of a heat conduction matrix material is characterized in that, comprises the steps:
According to massfraction 0.3 part ~ 1.5 parts coupling agent is dissolved in and is mixed with the alcohol solution that concentration is 3mg/mL ~ 15mg/mL in the alcohol-water mixture, according to massfraction 30 parts ~ 50 parts inorganic heat conduction particle is dispersed in water and obtains the suspension that concentration is 150mg/mL ~ 300mg/mL, take out after with described alcohol solution and described suspension mixing 1.5h ~ 3h dry at 50 ℃ ~ 70 ℃, described coupling agent is adsorbed on inorganic heat conduction particle surface, obtains the modified inorganic thermally conductive material;
According to massfraction under 55 ℃ ~ 65 ℃ with 100 parts Resins, epoxy, 20 parts ~ 30 parts reactive thinner and 30 parts ~ 50 parts described modified inorganic thermally conductive material mixing, obtain intermediate product, the organic solvent that then at room temperature adds 10 parts ~ 15 parts to described intermediate product, grind behind the mixing and carry out the vacuum outgas bubble and process, obtain component A;
At room temperature 30 parts ~ 45 parts solidifying agent is distributed to according to massfraction in 10 parts ~ 15 parts the described organic solvent, obtains B component; And
Described component A and described B component mixing after fixing are formed described heat conduction matrix material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210365882.2A CN102876272B (en) | 2012-09-27 | 2012-09-27 | Heat-conduction binding material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210365882.2A CN102876272B (en) | 2012-09-27 | 2012-09-27 | Heat-conduction binding material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102876272A true CN102876272A (en) | 2013-01-16 |
| CN102876272B CN102876272B (en) | 2014-10-29 |
Family
ID=47477801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210365882.2A Expired - Fee Related CN102876272B (en) | 2012-09-27 | 2012-09-27 | Heat-conduction binding material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102876272B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449510A (en) * | 2014-12-08 | 2015-03-25 | 成都锦汇科技有限公司 | Flexible heat-conduction epoxy resin adhesive and preparation method thereof |
| CN104877612A (en) * | 2015-06-15 | 2015-09-02 | 南京工业大学 | Heat-conducting insulating adhesive and preparation method thereof |
| CN104945856A (en) * | 2015-07-14 | 2015-09-30 | 江苏兆鋆新材料股份有限公司 | High-transparency anti-yellowing epoxy resin composite material preparing method and application thereof |
| CN107151510A (en) * | 2017-06-16 | 2017-09-12 | 安徽康瑞高科新材料技术工程有限公司 | A kind of heat-conductive coating |
| CN109618426A (en) * | 2018-11-20 | 2019-04-12 | 海盐徐氏电控设备有限公司 | A kind of electric ripple type PTC heating block being easily installed |
| CN110373139A (en) * | 2019-07-25 | 2019-10-25 | 天长市京发铝业有限公司 | A kind of high thermal conductivity coefficient copper-clad plate adhesive glue |
| CN112725551A (en) * | 2021-01-05 | 2021-04-30 | 佛山市枫灿新材料科技有限公司 | Leather plating crystal liquid and preparation method thereof |
| CN113462200A (en) * | 2021-07-01 | 2021-10-01 | 本时智能技术发展(上海)有限公司 | Amino polymerization-resistant modified heat-conducting particle and preparation method thereof |
| CN113512386A (en) * | 2021-03-16 | 2021-10-19 | 山东光实能源有限公司 | Epoxy resin-based composite bonding material for solar power generation pavement |
| CN114045133A (en) * | 2021-11-24 | 2022-02-15 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Preparation method of high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2661530A1 (en) * | 2006-08-25 | 2008-02-28 | Sachtleben Chemie Gmbh | Titanium dioxide-containing composite |
| JP2010131789A (en) * | 2008-12-02 | 2010-06-17 | Taisei Plas Co Ltd | Adhesion composite containing metal alloy, and method for producing the same |
| JP2011006544A (en) * | 2009-06-24 | 2011-01-13 | Taisei Plas Co Ltd | One-part epoxy adhesive and method of bonding |
| CN102660212A (en) * | 2012-06-08 | 2012-09-12 | 焦作市卓立烫印材料有限公司 | Single-component epoxy heat-conducting adhesive |
| CN102660213A (en) * | 2012-06-08 | 2012-09-12 | 焦作市卓立烫印材料有限公司 | Surface treatment method of heat-conducting filler for epoxy heat-conducting adhesive |
-
2012
- 2012-09-27 CN CN201210365882.2A patent/CN102876272B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2661530A1 (en) * | 2006-08-25 | 2008-02-28 | Sachtleben Chemie Gmbh | Titanium dioxide-containing composite |
| JP2010131789A (en) * | 2008-12-02 | 2010-06-17 | Taisei Plas Co Ltd | Adhesion composite containing metal alloy, and method for producing the same |
| JP2011006544A (en) * | 2009-06-24 | 2011-01-13 | Taisei Plas Co Ltd | One-part epoxy adhesive and method of bonding |
| CN102660212A (en) * | 2012-06-08 | 2012-09-12 | 焦作市卓立烫印材料有限公司 | Single-component epoxy heat-conducting adhesive |
| CN102660213A (en) * | 2012-06-08 | 2012-09-12 | 焦作市卓立烫印材料有限公司 | Surface treatment method of heat-conducting filler for epoxy heat-conducting adhesive |
Non-Patent Citations (1)
| Title |
|---|
| [加]GEORGE WYPYCH编著，程斌等译: "《填料手册》", 28 February 2003, article "填料的表面改性" * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449510A (en) * | 2014-12-08 | 2015-03-25 | 成都锦汇科技有限公司 | Flexible heat-conduction epoxy resin adhesive and preparation method thereof |
| CN104877612A (en) * | 2015-06-15 | 2015-09-02 | 南京工业大学 | Heat-conducting insulating adhesive and preparation method thereof |
| CN104945856A (en) * | 2015-07-14 | 2015-09-30 | 江苏兆鋆新材料股份有限公司 | High-transparency anti-yellowing epoxy resin composite material preparing method and application thereof |
| CN107151510A (en) * | 2017-06-16 | 2017-09-12 | 安徽康瑞高科新材料技术工程有限公司 | A kind of heat-conductive coating |
| CN109618426A (en) * | 2018-11-20 | 2019-04-12 | 海盐徐氏电控设备有限公司 | A kind of electric ripple type PTC heating block being easily installed |
| CN110373139A (en) * | 2019-07-25 | 2019-10-25 | 天长市京发铝业有限公司 | A kind of high thermal conductivity coefficient copper-clad plate adhesive glue |
| CN112725551A (en) * | 2021-01-05 | 2021-04-30 | 佛山市枫灿新材料科技有限公司 | Leather plating crystal liquid and preparation method thereof |
| CN113512386A (en) * | 2021-03-16 | 2021-10-19 | 山东光实能源有限公司 | Epoxy resin-based composite bonding material for solar power generation pavement |
| CN113462200A (en) * | 2021-07-01 | 2021-10-01 | 本时智能技术发展(上海)有限公司 | Amino polymerization-resistant modified heat-conducting particle and preparation method thereof |
| CN114045133A (en) * | 2021-11-24 | 2022-02-15 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Preparation method of high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102876272B (en) | 2014-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102876272B (en) | Heat-conduction binding material and preparation method thereof | |
| CN109913185A (en) | A kind of multilayered structure heat-conductive composite material and preparation method thereof containing heat conducting film | |
| CN110054864B (en) | High-thermal-conductivity composite filler and preparation method of polymer-based composite material thereof | |
| CN104830031B (en) | A kind of epoxy resin composite material and preparation method thereof having both heat conduction and antistatic property | |
| CN102770956B (en) | Thermosetting resin composition, b-stage thermally conductive sheet, and power module | |
| CN102290384B (en) | Insulating component, metallic substrates substrate, semiconductor module and manufacture method thereof | |
| CN104098982B (en) | Electrical equipment coating material, the manufacture method of electrical equipment coating material and hermetic type seal | |
| CN104673160A (en) | Filled surface modified silicon carbide isotropic thermal conduction adhesive and preparation method thereof | |
| CN106380848A (en) | Low-dielectric-constant high-thermal-conductivity silicone rubber composite material and preparation method thereof | |
| CN105505327B (en) | A kind of preparation method of carbon nanotube encapsulation paraffin phase change material | |
| CN106589820B (en) | A kind of multiphase composite material with high dielectric constant and preparation method thereof with isolation structure | |
| CN103080265A (en) | High performance die attach adhesives (DAAs) nanomaterials for high brightness LED | |
| CN103374207A (en) | Epoxy composite material and preparation method thereof | |
| CN105924952A (en) | Heat conductive and insulating composite material for LED and preparation method thereof | |
| CN105704911A (en) | High-thermal conductivity aluminum base circuit board manufacturing method | |
| KR101294593B1 (en) | Electrical conductive adhesives and fabrication method therof | |
| CN113881190A (en) | Epoxy resin composite material for packaging power electronic transformer and preparation method thereof | |
| CN103642422A (en) | Reparative conductive adhesive and preparation method thereof | |
| CN105461963A (en) | Surface-organically-modified boron nitride powder, preparation method and applications thereof | |
| JP6327549B2 (en) | Thermosetting resin composition and heat conductive sheet | |
| JP5526027B2 (en) | Amorphous siliceous powder, method for producing the same, resin composition, and semiconductor sealing material | |
| CN106751477A (en) | A kind of high-molecular-weight epoxy Heat Conduction Material and preparation method thereof | |
| CN107459775B (en) | A kind of epoxy resins insulation heat-conductive composite material and preparation method thereof | |
| CN105647345A (en) | High thermal conductivity aluminum substrate | |
| CN109161051B (en) | Modified hexagonal boron nitride and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141029 Termination date: 20210927 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |