CN117186796A - High-heat-conductivity polyacrylate pressure-sensitive adhesive and preparation method thereof - Google Patents
High-heat-conductivity polyacrylate pressure-sensitive adhesive and preparation method thereof Download PDFInfo
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- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 70
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000000945 filler Substances 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 239000004593 Epoxy Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 53
- 229910052582 BN Inorganic materials 0.000 claims description 52
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 35
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 30
- 229910052709 silver Inorganic materials 0.000 claims description 30
- 239000004332 silver Substances 0.000 claims description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 19
- 238000000498 ball milling Methods 0.000 claims description 16
- 239000007822 coupling agent Substances 0.000 claims description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 11
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 11
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 11
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 11
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 9
- 229920002799 BoPET Polymers 0.000 claims description 9
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 9
- 125000003700 epoxy group Chemical group 0.000 claims description 9
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-BJUDXGSMSA-N Boron-10 Chemical group [10B] ZOXJGFHDIHLPTG-BJUDXGSMSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 3
- -1 acrylic ester Chemical class 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 39
- 239000000203 mixture Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 5
- 239000011231 conductive filler Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229910052580 B4C Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Abstract
The invention discloses a high-heat-conductivity acrylic ester pressure-sensitive adhesive and a preparation method thereof. The high-heat-conductivity polyacrylate pressure-sensitive adhesive is prepared by uniformly ultrasonic mixing 60-80 parts by mass of polyacrylate solution, 3-10 parts by mass of epoxy tackifying resin, 5-10 parts by mass of modified heat-conducting filler and 0.3-1.0 part by mass of cross-linking agent, and then coating and drying.
Description
Technical Field
The invention relates to the field of pressure-sensitive adhesives, in particular to a high-heat-conductivity polyacrylate pressure-sensitive adhesive and a preparation method thereof.
Background
Aiming at the application requirements of electronic equipment with increasingly integrated, miniaturized and high-density electronic equipment, higher requirements are put on functional pressure-sensitive adhesives. In particular, electronic devices often release a large amount of heat during operational use, not only reducing the efficiency of the device, but also potentially causing the device to fail due to high temperatures. Based on the above, polyacrylate pressure-sensitive adhesives with heat conduction function are developed to meet the application requirements of high-performance miniaturized electronic equipment.
However, due to the specificity of the electronic device, the pressure-sensitive adhesive is required to have good heat conducting property and maintain original electrical insulation. Commercially available thermally conductive filler materials such as: silver, gold, iron, copper, graphite, etc., while having good heat conductive properties, often accompanies electrical conduction and easily causes short circuits of electronic devices in use, and based on this, development of insulating pressure-sensitive adhesives with high heat conductivity has attracted attention.
Common heat-conducting filling materials used for the heat-conducting insulating adhesive tape mainly comprise aluminum oxide, boron nitride, silicon nitride and the like, and the materials not only can endow the pressure-sensitive adhesive with good heat-conducting property, but also can keep the original insulativity of the pressure-sensitive adhesive. Compared with other heat-conducting electric materials, the boron nitride has excellent heat-conducting performance and good electric insulation performance, and is an ideal heat-conducting insulating filler. To obtain a pressure-sensitive adhesive with high thermal conductivity, a large amount of boron nitride is often required to be added, which greatly reduces the performance of the pressure-sensitive adhesive, and leads to unstable stripping performance in the use process of the thermal-conductive pressure-sensitive adhesive. Meanwhile, the addition of a large amount of boron nitride can also lead to uneven dispersion of the filler, and further worsen the performance of the pressure-sensitive adhesive. In addition, the addition of these thermally conductive fillers also increases the viscosity of the polyacrylate solution, making the pressure sensitive adhesive thickness unstable after coating.
Disclosure of Invention
The invention aims to provide a heat-conducting polyacrylate pressure-sensitive adhesive with high heat conduction, insulation and excellent stripping performance and a preparation method thereof, aiming at the defects of the existing high heat-conducting polyacrylate pressure-sensitive adhesive.
The invention aims at realizing the following technical scheme: the high-heat-conductivity-resistant polyacrylate pressure-sensitive adhesive consists of the following components:
60-80 parts by mass of polyacrylate solution;
3 to 10 parts by mass of an epoxidized tackifying resin;
5-10 parts by mass of modified heat conducting filler;
0.3 to 1.0 part by mass of a crosslinking agent.
The modified heat conduction filler is formed by mixing 45-65 parts by mass of modified micron boron nitride, 15-25 parts by mass of modified nanometer boron nitride and 10-40 parts by mass of modified dendritic silver coated copper.
The grain diameter of the micron boron nitride is 15-30 mu m, the grain diameter of the nanometer boron nitride is 50-500 nm, the grain diameter of the dendritic silver-coated copper powder is 5-25 mu m, and the silver content is 5% -20%;
the polyacrylate solution is prepared from 30 to 50 parts by mass of butyl acrylate, 4 to 8 parts by mass of vinyl acetate, 10 to 20 parts by mass of ethyl acetate, 30 to 40 parts by mass of toluene, 0.24 to 0.45 part by mass of azobisisobutyronitrile, 0.1 to 0.3 part by mass of hydroxyethyl acrylate, 0.2 to 1.2 parts by mass of acrylic acid and 1 to 3 parts by mass of glycidyl methacrylate through free radical polymerization.
The modified tackifying resin is epoxy acrylate rosin resin, the epoxy group content is 0.2-1.5%, and the softening point is 60-90 ℃.
The cross-linking agent is one of toluene diisocyanate and hexamethylene diisocyanate.
The preparation method of the high-heat-conductivity polyacrylate pressure-sensitive adhesive is characterized by comprising the following steps of: uniformly mixing 60-80 parts by mass of polyacrylate solution, 3-10 parts by mass of epoxy tackifying resin, 5-10 parts by mass of modified heat conducting filler and 0.3-1.0 part by mass of cross-linking agent by ultrasound, coating on a PET film, drying, and transferring to an oven for curing to obtain the modified heat conducting resin.
The preparation method of the high-heat-conductivity polyacrylate pressure-sensitive adhesive is characterized in that the polyacrylate solution is obtained by a solution polymerization method, and the preparation method comprises the following steps:
(1) Uniformly mixing 30-50 parts by mass of butyl acrylate, 10-20 parts by mass of ethyl acetate, 30-40 parts by mass of toluene, 0.18-0.36 part by mass of azodiisobutyronitrile, 0.1-0.3 part by mass of hydroxyethyl acrylate and 0.2-1.2 parts by mass of acrylic acid, and heating to 65-80 ℃ for reacting for 1.5-2.5 hours;
(2) Adding 4-8 parts by mass of vinyl acetate, 1-3 parts by mass of glycidyl methacrylate and 0.06-0.09 part by mass of azodiisobutyronitrile, continuously reacting for 1.5-2 hours, heating to 85 ℃, continuously reacting for 1 hour, and cooling to room temperature to obtain the polyacrylic acid solution.
The preparation method of the high-heat-conductivity polyacrylate pressure-sensitive adhesive is characterized by comprising the following steps of: adding 45-65 parts by mass of micrometer boron nitride and 15-25 parts by mass of nanometer boron nitride into a ball mill, synchronously dripping 0.5-3.0 parts by mass of gamma-aminopropyl triethoxysilane coupling agent, ball-milling to obtain modified micrometer boron nitride and modified nanometer boron nitride, then adding 10-40 parts by mass of modified dendritic silver coated copper, dripping 0.1-0.5 part by mass of 3-glycidoxypropyl trimethoxysilane coupling agent, and ball-milling to obtain the modified heat conducting filler.
By mixing the micron boron nitride and the nanometer boron nitride, the nanometer boron nitride can be filled into the gap of the micron boron nitride, and the heat conduction efficiency of the nanometer boron nitride is improved; the introduced dendritic silver-coated copper can fully exert the high heat conduction performance of the silver-coated copper, and further improve the pressure-sensitive excellent heat conduction performance; meanwhile, the existence of the boron nitride can keep the system to maintain good electrical insulation performance, and the use amount of the heat-conducting filler of the pressure-sensitive adhesive system is reduced. In addition, through a surface modification mode, the content of surface hydroxyl groups of the inorganic powder can be reduced, so that the coating property of a polyacrylate solution system is improved, amino modified boron nitride and epoxy modified dendritic silver coated copper can be subjected to chemical reaction with the epoxidized polyacrylate, the compatibility and the binding force of a heat conducting filler system and polyacrylate resin are improved, and the high-performance heat conducting polyacrylate pressure-sensitive adhesive is obtained.
Compared with the prior art, the invention has the following advantages:
(1) The prepared heat-conducting pressure-sensitive adhesive has good stripping performance and insulating performance;
(2) The prepared heat-conducting pressure-sensitive adhesive has excellent heat-conducting property.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to examples, but the embodiments of the present invention are not limited thereto.
Drawings
FIG. 1 is a scanning electron microscope image of a modified thermally conductive filler.
Example 1
Preparation of modified polyacrylate solution:
(1) After nitrogen replacement, 40 parts by mass of butyl acrylate, 15 parts by mass of ethyl acetate, 40 parts by mass of toluene, 0.24 part by mass of azobisisobutyronitrile, 0.2 part by mass of hydroxyethyl acrylate and 0.8 part by mass of acrylic acid are uniformly mixed in a reaction bottle provided with a thermometer and a stirring paddle, and then added into the reaction bottle to be heated to 80 ℃ for reaction for 2.5 hours;
(2) 6 parts by mass of vinyl acetate, 1.8 parts by mass of glycidyl methacrylate and 0.09 part by mass of azobisisobutyronitrile are continuously added into a reaction bottle, the reaction is continued for 2 hours, the temperature is raised to 85 ℃, the reaction is continued for 1 hour, and the temperature is reduced to room temperature, so as to obtain the polyacrylate solution.
Preparation of modified heat conducting filler:
adding 50 parts by mass of micrometer boron nitride and 20 parts by mass of nanometer boron nitride into a ball mill, controlling the ball milling speed to be 2000r/min, synchronously dripping 1.5 parts by mass of gamma-aminopropyl triethoxysilane coupling agent, obtaining modified micrometer boron nitride and modified nanometer boron nitride after 5min, then adding 25 parts by mass of modified dendritic silver coated copper (20 mu m, silver content is 16%), dripping 0.3 parts by mass of 3-glycidol ether oxypropyl trimethoxysilane coupling agent, and obtaining the modified heat conducting filler after ball milling treatment.
Preparation of high-heat-conductivity polyacrylate pressure-sensitive adhesive:
after uniformly mixing 70 parts by mass of polyacrylate solution, 8 parts by mass of epoxidized acrylate rosin resin (the epoxy group content is 0.8%, and the softening point is 80 ℃), 8 parts by mass of modified heat-conducting filler and 0.7 part by mass of toluene diisocyanate by ultrasound, standing until no obvious bubble is generated, uniformly coating the mixture on a PET film by using a coating machine, controlling the dry adhesive thickness to be 25 mu m plus or minus 2 mu m, transferring the mixture into a 160 ℃ oven for 5min, and transferring the mixture into a 90 ℃ oven for curing for 24h to obtain the high heat-conducting polyacrylate pressure-sensitive adhesive.
Fig. 1 is an SEM photograph of the modified heat conductive filler prepared in example 1. It can be seen that the micron-sized boron nitride and the nanometer-sized boron nitride are dispersed in the dendritic silver-coated copper to form a continuous heat conduction path, and the existence of the boron carbide also blocks the dendritic silver-coated copper to form the heat conduction path.
Example 2
Preparation of modified polyacrylate solution:
(1) After nitrogen replacement, 30 parts by mass of butyl acrylate, 10 parts by mass of ethyl acetate, 10 parts by mass of toluene, 0.18 part by mass of azobisisobutyronitrile, 0.1 part by mass of hydroxyethyl acrylate and 0.2 part by mass of acrylic acid are uniformly mixed in a reaction bottle provided with a thermometer and a stirring paddle, and then added into the reaction bottle to be heated to 75 ℃ for reaction for 2 hours;
(2) Continuously adding 4 parts by mass of vinyl acetate, 1 part by mass of glycidyl methacrylate and 0.06 part by mass of azobisisobutyronitrile into a reaction bottle, continuously reacting for 2 hours, heating to 85 ℃, continuously reacting for 1 hour, and cooling to room temperature to obtain a polyacrylate solution.
Preparation of modified heat conducting filler:
adding 45 parts by mass of micrometer boron nitride and 15 parts by mass of nanometer boron nitride into a ball mill, controlling the ball milling speed to 1600r/min, synchronously dripping 0.5 part by mass of gamma-aminopropyl triethoxysilane coupling agent, obtaining modified micrometer boron nitride and modified nanometer boron nitride after 5min, then adding 10 parts by mass of modified dendritic silver coated copper (5 mu m, 20% of silver content), dripping 0.1 part by mass of 3-glycidol ether oxypropyl trimethoxysilane coupling agent, and obtaining the modified heat conducting filler after ball milling treatment.
Preparation of high-heat-conductivity polyacrylate pressure-sensitive adhesive:
uniformly mixing 80 parts by mass of polyacrylate solution, 10 parts by mass of epoxy acrylate rosin resin (the epoxy group content is 1.5%, and the softening point is 90 ℃), 10 parts by mass of modified heat conducting filler and 0.6 part by mass of hexamethylene diisocyanate by ultrasound, standing until no obvious bubble is generated, uniformly coating the mixture on a PET film by using a coating machine, controlling the thickness of dry adhesive to be 25 mu m plus or minus 2 mu m, transferring the mixture into a 160 ℃ oven for 5min, and transferring the mixture into a 90 ℃ oven for curing for 24h to obtain the high heat conducting polyacrylate pressure-sensitive adhesive.
Example 3
Preparation of modified polyacrylate solution:
(1) After nitrogen replacement, 50 parts by mass of butyl acrylate, 20 parts by mass of ethyl acetate, 40 parts by mass of toluene, 0.36 part by mass of azobisisobutyronitrile, 0.3 part by mass of hydroxyethyl acrylate and 1.2 parts by mass of acrylic acid are uniformly mixed in a reaction bottle provided with a thermometer and a stirring paddle, and then the mixture is added into the reaction bottle to be heated to 65 ℃ for reaction for 2.5 hours;
(2) 8 parts by mass of vinyl acetate, 3 parts by mass of glycidyl methacrylate and 0.09 part by mass of azobisisobutyronitrile are continuously added into a reaction bottle, the reaction is continued for 1.5 hours, the temperature is raised to 85 ℃, the reaction is continued for 1 hour, and the temperature is reduced to room temperature, so as to obtain the polyacrylate solution.
Preparation of modified heat conducting filler:
adding 65 parts by mass of micrometer boron nitride and 25 parts by mass of nanometer boron nitride into a ball mill, controlling the ball milling speed to 1800r/min, synchronously dripping 3.0 parts by mass of gamma-aminopropyl triethoxysilane coupling agent, obtaining modified micrometer boron nitride and modified nanometer boron nitride after 5min, then adding 40 parts by mass of modified dendritic silver coated copper (25 mu m, silver content is 5%), dripping 0.5 part by mass of 3-glycidol ether oxypropyl trimethoxysilane coupling agent, and obtaining the modified heat conducting filler after ball milling treatment.
Preparation of high-heat-conductivity polyacrylate pressure-sensitive adhesive:
60 parts by mass of polyacrylate solution, 3 parts by mass of epoxidized acrylate rosin resin (the epoxy group content is 0.2%, and the softening point is 60 ℃), 5 parts by mass of modified heat-conducting filler and 1.0 part by mass of toluene diisocyanate are uniformly mixed by ultrasonic, and then placed until no obvious bubble is generated, the mixture is uniformly coated on a PET film by using a coating machine, the dry adhesive thickness is controlled to be 25 mu m plus or minus 2 mu m, then the mixture is transferred to a 160 ℃ oven for 5min, and then transferred to a 90 ℃ oven for curing for 24 hours, so that the high heat-conducting polyacrylate pressure-sensitive adhesive is obtained.
Example 4
Preparation of modified polyacrylate solution:
(1) In a reaction bottle provided with a thermometer and a stirring paddle, after nitrogen replacement, 45 parts by mass of butyl acrylate, 18 parts by mass of ethyl acetate, 36 parts by mass of toluene, 0.22 part by mass of azobisisobutyronitrile, 0.2 part by mass of hydroxyethyl acrylate and 1.2 parts by mass of acrylic acid are uniformly mixed, and then added into the reaction bottle to be heated to 75 ℃ for reaction for 1.5 hours;
(2) Continuously adding 5 parts by mass of vinyl acetate, 2.4 parts by mass of glycidyl methacrylate and 0.08 part by mass of azodiisobutyronitrile into a reaction bottle, continuously reacting for 1.5 hours, heating to 85 ℃, continuously reacting for 1 hour, and cooling to room temperature to obtain a polyacrylate solution.
Preparation of modified heat conducting filler:
adding 55 parts by mass of micrometer boron nitride and 15 parts by mass of nanometer boron nitride into a ball mill, controlling the ball milling speed to be 1200r/min, synchronously dripping 2.4 parts by mass of gamma-aminopropyl triethoxysilane coupling agent, obtaining modified micrometer boron nitride and modified nanometer boron nitride after 8min, then adding 12 parts by mass of modified dendritic silver coated copper (12 mu m, silver content is 16%), dripping 0.1 part by mass of 3-glycidol ether oxypropyl trimethoxysilane coupling agent, and obtaining the modified heat conducting filler after ball milling treatment.
Preparation of high-heat-conductivity polyacrylate pressure-sensitive adhesive:
after 75 parts by mass of polyacrylate solution, 8 parts by mass of epoxidized acrylate rosin resin (the epoxy group content is 0.9%, and the softening point is 78 ℃), 9 parts by mass of modified heat-conducting filler and 0.3 part by mass of toluene diisocyanate are uniformly mixed by ultrasonic, the mixture is placed until no obvious bubble is generated, the mixture is uniformly coated on a PET film by using a coating machine, the thickness of dry adhesive is controlled to be 25 mu m plus or minus 2 mu m, the mixture is then transferred to a 160 ℃ oven for 5min, and then transferred to a 90 ℃ oven for curing for 24h, so that the high heat-conducting polyacrylate pressure-sensitive adhesive is obtained.
Example 5
Preparation of modified polyacrylate solution:
(1) In a reaction bottle provided with a thermometer and a stirring paddle, after nitrogen replacement, 45 parts by mass of butyl acrylate, 15 parts by mass of ethyl acetate, 36 parts by mass of toluene, 0.21 part by mass of azobisisobutyronitrile, 0.1 part by mass of hydroxyethyl acrylate and 0.9 part by mass of acrylic acid are uniformly mixed, and then added into the reaction bottle to be heated to 75 ℃ for reaction for 2 hours;
(2) 8 parts by mass of vinyl acetate, 1 part by mass of glycidyl methacrylate and 0.06 part by mass of azobisisobutyronitrile are continuously added into a reaction bottle, the reaction is continued for 2 hours, the temperature is raised to 85 ℃, the reaction is continued for 1 hour, and the temperature is reduced to room temperature, so as to obtain the polyacrylate solution.
Preparation of modified heat conducting filler:
adding 45 parts by mass of micrometer boron nitride and 25 parts by mass of nanometer boron nitride into a ball mill, controlling the ball milling speed to 2200r/min, synchronously dripping 3.0 parts by mass of gamma-aminopropyl triethoxysilane coupling agent, obtaining modified micrometer boron nitride and modified nanometer boron nitride after 4min, then adding 30 parts by mass of modified dendritic silver coated copper (12 mu m, silver content is 9%), dripping 0.4 parts by mass of 3-glycidol ether oxypropyl trimethoxysilane coupling agent, and obtaining the modified heat conducting filler after ball milling treatment.
Preparation of high-heat-conductivity polyacrylate pressure-sensitive adhesive:
uniformly mixing 80 parts by mass of polyacrylate solution, 10 parts by mass of epoxy acrylate rosin resin (the epoxy group content is 1.5%, and the softening point is 68 ℃), 10 parts by mass of modified heat conducting filler and 0.7 part by mass of hexamethylene diisocyanate by ultrasound, standing until no obvious bubble is generated, uniformly coating the mixture on a PET film by using a coating machine, controlling the thickness of dry adhesive to be 25 mu m plus or minus 2 mu m, transferring the mixture into a 160 ℃ oven for 5min, and transferring the mixture into a 90 ℃ oven for curing for 24h to obtain the high heat conducting polyacrylate pressure-sensitive adhesive.
Comparative example 1
Preparation of modified polyacrylate solution:
(1) After nitrogen replacement, 40 parts by mass of butyl acrylate, 15 parts by mass of ethyl acetate, 40 parts by mass of toluene, 0.24 part by mass of azobisisobutyronitrile, 0.2 part by mass of hydroxyethyl acrylate and 0.8 part by mass of acrylic acid are uniformly mixed in a reaction bottle provided with a thermometer and a stirring paddle, and then added into the reaction bottle to be heated to 80 ℃ for reaction for 2.5 hours;
(2) 6 parts by mass of vinyl acetate, 1.8 parts by mass of glycidyl methacrylate and 0.09 part by mass of azobisisobutyronitrile are continuously added into a reaction bottle, the reaction is continued for 2 hours, the temperature is raised to 85 ℃, the reaction is continued for 1 hour, and the temperature is reduced to room temperature, so as to obtain the polyacrylate solution.
Preparation of modified heat conducting filler:
50 parts by mass of micron boron nitride, 20 parts by mass of nano boron nitride and 25 parts by mass of modified dendritic silver coated copper (20 mu m, silver content is 16%) are added into a ball mill, and the ball milling speed is controlled to be 2000r/min, so that the modified heat conduction filler is obtained after 5 min.
Preparation of high-heat-conductivity polyacrylate pressure-sensitive adhesive:
after uniformly mixing 70 parts by mass of polyacrylate solution, 8 parts by mass of epoxidized acrylate rosin resin (the epoxy group content is 0.8%, and the softening point is 80 ℃), 8 parts by mass of modified heat-conducting filler and 0.7 part by mass of toluene diisocyanate by ultrasound, standing until no obvious bubble is generated, uniformly coating the mixture on a PET film by using a coating machine, controlling the dry adhesive thickness to be 25 mu m plus or minus 2 mu m, transferring the mixture into a 160 ℃ oven for 5min, and transferring the mixture into a 90 ℃ oven for curing for 24h to obtain the high heat-conducting polyacrylate pressure-sensitive adhesive.
Comparative example 2
Preparation of modified polyacrylate solution:
(1) After nitrogen replacement, 40 parts by mass of butyl acrylate, 15 parts by mass of ethyl acetate, 40 parts by mass of toluene, 0.24 part by mass of azobisisobutyronitrile, 0.2 part by mass of hydroxyethyl acrylate and 0.8 part by mass of acrylic acid are uniformly mixed in a reaction bottle provided with a thermometer and a stirring paddle, and then added into the reaction bottle to be heated to 80 ℃ for reaction for 2.5 hours;
(2) 6 parts by mass of vinyl acetate, 1.8 parts by mass of glycidyl methacrylate and 0.09 part by mass of azobisisobutyronitrile are continuously added into a reaction bottle, the reaction is continued for 2 hours, the temperature is raised to 85 ℃, the reaction is continued for 1 hour, and the temperature is reduced to room temperature, so as to obtain the polyacrylate solution.
Preparation of modified heat conducting filler:
70 parts by mass of micrometer boron nitride and 25 parts by mass of modified dendritic silver coated copper (20 mu m, silver content is 16%) are added into a ball mill, the ball milling speed is controlled to be 2000r/min, and 1.5 parts by mass of gamma-aminopropyl triethoxysilane coupling agent is synchronously added dropwise, so that the modified heat conducting filler is obtained after 5 min.
Preparation of high-heat-conductivity polyacrylate pressure-sensitive adhesive:
after uniformly mixing 70 parts by mass of polyacrylate solution, 8 parts by mass of epoxidized acrylate rosin resin (the epoxy group content is 0.8%, and the softening point is 80 ℃), 8 parts by mass of modified heat-conducting filler and 0.7 part by mass of toluene diisocyanate by ultrasound, standing until no obvious bubble is generated, uniformly coating the mixture on a PET film by using a coating machine, controlling the dry adhesive thickness to be 25 mu m plus or minus 2 mu m, transferring the mixture into a 160 ℃ oven for 5min, and transferring the mixture into a 90 ℃ oven for curing for 24h to obtain the high heat-conducting polyacrylate pressure-sensitive adhesive.
Fig. 1 is an SEM photograph of the modified heat conductive filler prepared in example 1. It can be seen that the micron-sized boron nitride and the nanometer-sized boron nitride are dispersed in the dendritic silver-coated copper to form a continuous heat conduction path, and the existence of the boron carbide also blocks the dendritic silver-coated copper to form the heat conduction path.
Test method
Peel strength test: reference is made to GB/T2792-1998 (180℃peel strength test method for pressure-sensitive adhesive tape). SUS304 stainless steel plate with specially treated surface is selected as the adherend.
And (3) testing the holding power: the tape holding test is determined with reference to GB/T4851-2014, and the time to failure of the tape under load is tested.
And (3) testing heat conduction performance: the DRL-III type heat conductivity coefficient tester has the test standard of GB/T10294-2008, the test method is a hot flow method, the cold electrode temperature is set to 20 ℃, and the hot electrode temperature is set to 60 ℃.
Resistance test: the resistance between the two points of the tape was tested using a multimeter (contact measurement).
Table 1 results of performance tests of examples and comparative examples
As can be seen from the performance tests of the examples and the comparative examples in Table 1, the high thermal conductivity polyacrylate pressure sensitive adhesive obtained in examples 1 to 5 not only has higher peel strength, but also has better holding power, heat conduction performance reaching 0.93W/(m.K), better insulating performance, and resistance of 4.1 x 10 6 Ω。
Comparative example 1 has poor peel strength and holding power, and poor heat conductive properties, but has higher electrical resistance, as compared with example 1. While the comparative example 2 has higher resistance, but still has poorer peel strength and holding power, and the heat conduction performance is only 0.46W/(m.K), so the heat conduction polyacrylate pressure-sensitive adhesive obtained by the invention has higher peel strength, good holding power, excellent heat conduction performance and insulation, and solves the problems of large addition amount, poor heat conduction performance and unstable peel strength of common heat conduction polyacrylate pressure-sensitive adhesive filler.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (8)
1. The high-heat-conductivity polyacrylate pressure-sensitive adhesive is characterized by comprising the following components:
60-80 parts by mass of polyacrylate solution;
3 to 10 parts by mass of an epoxidized tackifying resin;
5-10 parts by mass of modified heat conducting filler;
0.3 to 1.0 part by mass of a crosslinking agent.
The modified heat conduction filler is formed by mixing 45-65 parts by mass of modified micron boron nitride, 15-25 parts by mass of modified nanometer boron nitride and 10-40 parts by mass of modified dendritic silver coated copper.
2. The high-heat-conductivity polyacrylate pressure-sensitive adhesive according to claim 1, wherein the particle size of the micron boron nitride is 15-30 μm, the particle size of the nanometer boron nitride is 50-500 nm, the particle size of the dendritic silver-coated copper powder is 5-25 μm, and the silver content is 5-20%.
3. The high thermal conductivity polyacrylate pressure-sensitive adhesive according to claim 1, wherein the polyacrylate solution is obtained by radical polymerization from 30 to 50 parts by mass of butyl acrylate, 4 to 8 parts by mass of vinyl acetate, 10 to 20 parts by mass of ethyl acetate, 30 to 40 parts by mass of toluene, 0.24 to 0.45 part by mass of azobisisobutyronitrile, 0.1 to 0.3 part by mass of hydroxyethyl acrylate, 0.2 to 1.2 parts by mass of acrylic acid and 1 to 3 parts by mass of glycidyl methacrylate.
4. The high thermal conductivity polyacrylate pressure sensitive adhesive according to claim 1, wherein the modified tackifying resin is an epoxidized acrylate rosin resin, the epoxy group content is 0.2-1.5%, and the softening point is 60-90 ℃.
5. The high thermal conductivity polyacrylate pressure sensitive adhesive of claim 1, wherein the cross-linking agent is one of toluene diisocyanate and hexamethylene diisocyanate.
6. The method for preparing the high-heat-conductivity polyacrylate pressure-sensitive adhesive according to any one of claims 1 to 5, which is characterized in that: uniformly mixing 60-80 parts by mass of polyacrylate solution, 3-10 parts by mass of epoxy tackifying resin, 5-10 parts by mass of modified heat conducting filler and 0.3-1.0 part by mass of cross-linking agent by ultrasound, coating on a PET film, drying, and transferring to an oven for curing to obtain the modified heat conducting resin.
7. The method for preparing the high-thermal-conductivity polyacrylate pressure-sensitive adhesive according to claim 6, wherein the polyacrylate solution is obtained by a solution polymerization method, and the preparation method comprises the following steps:
(1) Uniformly mixing 30-50 parts by mass of butyl acrylate, 10-20 parts by mass of ethyl acetate, 30-40 parts by mass of toluene, 0.18-0.36 part by mass of azodiisobutyronitrile, 0.1-0.3 part by mass of hydroxyethyl acrylate and 0.2-1.2 parts by mass of acrylic acid, and heating to 65-80 ℃ for reacting for 1.5-2.5 hours;
(2) Adding 4-8 parts by mass of vinyl acetate, 1-3 parts by mass of glycidyl methacrylate and 0.06-0.09 part by mass of azodiisobutyronitrile, continuously reacting for 1.5-2 hours, heating to 85 ℃, continuously reacting for 1 hour, and cooling to room temperature to obtain the polyacrylic acid solution.
8. The method for preparing the high-heat-conductivity polyacrylate pressure-sensitive adhesive according to claim 6, wherein the preparation process of the modified heat-conductivity filler is as follows: adding 45-65 parts by mass of micrometer boron nitride and 15-25 parts by mass of nanometer boron nitride into a ball mill, synchronously dripping 0.5-3.0 parts by mass of gamma-aminopropyl triethoxysilane coupling agent, ball-milling to obtain modified micrometer boron nitride and modified nanometer boron nitride, then adding 10-40 parts by mass of modified dendritic silver coated copper, dripping 0.1-0.5 part by mass of 3-glycidoxypropyl trimethoxysilane coupling agent, and ball-milling to obtain the modified heat conducting filler.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117551405A (en) * | 2024-01-11 | 2024-02-13 | 宁波长阳科技股份有限公司 | Conductive polyacrylate pressure-sensitive adhesive and preparation method thereof |
| CN117551405B (en) * | 2024-01-11 | 2024-04-30 | 宁波长阳科技股份有限公司 | Conductive polyacrylate pressure-sensitive adhesive and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117551405A (en) * | 2024-01-11 | 2024-02-13 | 宁波长阳科技股份有限公司 | Conductive polyacrylate pressure-sensitive adhesive and preparation method thereof |
| CN117551405B (en) * | 2024-01-11 | 2024-04-30 | 宁波长阳科技股份有限公司 | Conductive polyacrylate pressure-sensitive adhesive and preparation method thereof |
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