CN110066494B - Epoxy resin composition, preparation method and application thereof, and aluminum-based copper-clad plate - Google Patents
Epoxy resin composition, preparation method and application thereof, and aluminum-based copper-clad plate Download PDFInfo
- Publication number
- CN110066494B CN110066494B CN201910376566.7A CN201910376566A CN110066494B CN 110066494 B CN110066494 B CN 110066494B CN 201910376566 A CN201910376566 A CN 201910376566A CN 110066494 B CN110066494 B CN 110066494B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- mass
- resin composition
- aluminum
- composition according
- 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.)
- Active
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 170
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 170
- 239000000203 mixture Substances 0.000 title claims abstract description 81
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 58
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000007787 solid Substances 0.000 claims abstract description 54
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims abstract description 53
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002904 solvent Substances 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 30
- 239000011256 inorganic filler Substances 0.000 claims abstract description 28
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 28
- 239000011787 zinc oxide Substances 0.000 claims abstract description 27
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 26
- 229920000570 polyether Polymers 0.000 claims abstract description 26
- 150000002148 esters Chemical class 0.000 claims abstract description 25
- 239000012745 toughening agent Substances 0.000 claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 32
- 239000011889 copper foil Substances 0.000 claims description 30
- 239000003292 glue Substances 0.000 claims description 30
- 239000004973 liquid crystal related substance Substances 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 239000004593 Epoxy Substances 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 15
- 238000007731 hot pressing Methods 0.000 claims description 14
- 239000000395 magnesium oxide Substances 0.000 claims description 14
- 239000007822 coupling agent Substances 0.000 claims description 13
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical group [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 13
- 229920000459 Nitrile rubber Polymers 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 claims description 10
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical group C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical group CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 9
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 150000002576 ketones Chemical group 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- 150000001408 amides Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 241000276450 Hucho Species 0.000 claims description 2
- 150000004982 aromatic amines Chemical group 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000005238 degreasing Methods 0.000 claims description 2
- 229920006287 phenoxy resin Polymers 0.000 claims description 2
- 239000013034 phenoxy resin Substances 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 238000010008 shearing Methods 0.000 claims 7
- 239000000853 adhesive Substances 0.000 claims 2
- 230000001070 adhesive effect Effects 0.000 claims 2
- 125000002883 imidazolyl group Chemical group 0.000 claims 1
- 238000010292 electrical insulation Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 18
- 230000017525 heat dissipation Effects 0.000 description 5
- 239000011324 bead Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004026 adhesive bonding Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 241000208152 Geranium Species 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 241000282376 Panthera tigris Species 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000010364 biochemical engineering Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- -1 polydimethylsiloxane Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0036—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/08—Interconnection of layers by mechanical means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V29/00—Protecting lighting devices from thermal damage; Cooling or heating arrangements specially adapted for lighting devices or systems
- F21V29/50—Cooling arrangements
- F21V29/502—Cooling arrangements characterised by the adaptation for cooling of specific components
- F21V29/508—Cooling arrangements characterised by the adaptation for cooling of specific components of electrical circuits
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V29/00—Protecting lighting devices from thermal damage; Cooling or heating arrangements specially adapted for lighting devices or systems
- F21V29/85—Protecting lighting devices from thermal damage; Cooling or heating arrangements specially adapted for lighting devices or systems characterised by the material
- F21V29/89—Metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/302—Conductive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21Y—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO THE FORM OR THE KIND OF THE LIGHT SOURCES OR OF THE COLOUR OF THE LIGHT EMITTED
- F21Y2115/00—Light-generating elements of semiconductor light sources
- F21Y2115/10—Light-emitting diodes [LED]
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Fluid Mechanics (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an epoxy resin composition, a preparation method and application thereof, and an aluminum-based copper-clad plate. The composition comprises the following components: solid epoxy resin, liquid epoxy resin, a toughening agent, a curing accelerator, inorganic filler, a solvent, tetrapod-like zinc oxide whiskers, a bisphenol A polyether ester block epoxy resin polymer and a polycarboxylic acid polymer. The epoxy resin composition has good heat resistance, thermal conductivity and electrical insulation, and the double-sided aluminum-based copper-clad plate prepared from the epoxy resin composition has good heat resistance, remarkably improves the thermal conductivity (the thermal conductivity coefficient can reach 2.3W/m.K at most) and the electrical insulation performance, effectively ensures the safety of LED products and prolongs the service life.
Description
Technical Field
The invention relates to an epoxy resin composition, a preparation method and application thereof, and an aluminum-based copper-clad plate.
Background
With the maturity of the LED manufacturing technology, the LED luminance is greatly improved, the lifetime is greatly improved, and the production cost is greatly reduced, so that the LED lighting is widely popularized and becomes a main lighting mode for replacing traditional light sources such as incandescent lamps. The photoelectric conversion efficiency of the high-power LED is low, and about 80% of input electric energy is converted into heat. Because the area of the LED chip is small, if the generated heat cannot be dissipated in time, the luminous efficiency is rapidly reduced, and the service life is also rapidly reduced. Thus, heat dissipation from high power LEDs is a problem that must be addressed.
The aluminum-based copper-clad plate is a composite material made of an aluminum plate, a heat-conducting insulating medium layer and a conductive copper foil and is used for manufacturing an aluminum-based printed circuit board. The LED lamp has excellent heat dissipation performance, electromagnetic shielding performance, machining performance and the like, and is widely applied to LED illumination, high-power electrical equipment, automobiles, power supply equipment and the like.
Therefore, the aluminum-based copper clad laminate is also generally used as a preferred material for heat dissipation of high-power LEDs. Two aluminum-based circuit boards for loading LED lamp beads and lamp bead driving are generally arranged in the existing LED lamp, the requirement on miniaturization of the lamp is higher and higher, and the installation mode of installing the LED lamp beads and the lamp bead driving on two sides of one aluminum-based circuit board is provided. The mounting mode has the greatest advantages that the miniaturization of the lamp is met, the service life of the lamp is not influenced, and the mounting mode is an ideal mounting mode. However, the double-sided mounting can cause the heat dissipation of the aluminum-based copper-clad plate to be poor, which affects the service life of the LED, while the conventional aluminum-based copper-clad plate is generally only suitable for single-sided mounting, and has poor heat resistance, which is difficult to meet the requirement of the double-sided mounting mode of the LED on the heat-conducting property.
Therefore, how to prepare the aluminum-based copper-clad plate with excellent heat conductivity, electrical insulation performance and heat resistance is a technical problem to be solved urgently in the field.
Disclosure of Invention
The invention aims to overcome the defects of poor heat dissipation performance and poor heat resistance of an aluminum-based copper-clad plate in the prior art, and provides an epoxy resin composition, a preparation method and application thereof and the aluminum-based copper-clad plate. The epoxy resin composition has good heat resistance, thermal conductivity and electrical insulation, and the aluminum-based copper-clad plate further prepared from the epoxy resin composition has high thermal stress and thermal conductivity, and the breakdown voltage can meet the use requirement.
The invention solves the technical problems through the following technical scheme.
The invention provides an epoxy resin composition, which comprises the following components: solid epoxy resin, liquid epoxy resin, a toughening agent, a curing accelerator, an inorganic filler, a solvent, tetrapod-like zinc oxide whiskers, a bisphenol A polyether ester liquid crystal block epoxy resin polymer and a polycarboxylic acid polymer, wherein:
the bisphenol A polyether ester liquid crystal block epoxy resin polymer manufacturer is a new material with the model of SGE 4816;
the polycarboxylic acid polymer manufacturer is a new hucho material with the model of SGR-003; the number average molecular weight of the polycarboxylic acid polymer is 2500-4000;
the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the tetrapod-like zinc oxide whisker is 100 (5-20);
the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the bisphenol A polyether ester liquid crystal block epoxy resin polymer is 100 (3-6);
the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the polycarboxylic acid polymer is 100 (0.3-0.5).
In the present invention, the solid epoxy resin may be a solid epoxy resin conventional in the art, such as bisphenol a glycidyl ether epoxy resin. The epoxy value of the bisphenol A glycidyl ether epoxy resin can be 0.20-0.25.
In the present invention, the amount of the solid epoxy resin may be an amount conventionally used in the art, for example, the mass ratio of the solid epoxy resin to the liquid epoxy resin is (1:4) to (4:1), and further, for example, 1:4, 2:3, 3:2 or 4: 1.
In the invention, the liquid epoxy resin can be a liquid epoxy resin which is conventional in the field, such as bisphenol A epoxy resin with the number average molecular weight of 300-500. The epoxy value of the bisphenol A epoxy resin with the number average molecular weight of 300-500 is preferably 0.40-0.55.
In the present invention, the toughening agent may be a toughening agent conventional in the art, such as one or more of random carboxylated nitrile rubber, polyvinyl butyral and phenoxy resin, preferably random carboxylated nitrile rubber. The random carboxylated nitrile rubber may have a number average molecular weight (Mn) of 20000 to 50000, for example 27500.
In the invention, the amount of the toughening agent can be the amount conventionally used in the art, for example, the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the toughening agent is 100 (5-15), and further, for example, 100:5, 100:8, 100:11 or 100: 14.
In the present invention, the curing agent may be a curing agent conventional in the art, such as an aromatic amine-based curing agent, and further such as diaminodiphenyl sulfone. The diaminodiphenyl sulfone can be analytically pure, and its purity is generally not less than 99.3%.
In the invention, the amount of the curing agent can be the amount conventionally used in the art, for example, the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the curing agent is 100 (15-30), and further, for example, 100:28, 100:24, 100:21 or 100: 18.
In the present invention, the curing accelerator may be a curing accelerator conventional in the art, such as an imidazole-based curing accelerator, and further such as 2-ethyl-4-methylimidazole. The purity of the 2-ethyl-4-methylimidazole may be chemically pure.
In the present invention, the amount of the curing accelerator may be an amount conventionally used in the art, for example, the mass ratio of the sum of the solid epoxy resin and the liquid epoxy resin to the curing accelerator is 100 (0.01 to 0.10), and further, for example, 100:0.025, 100:0.030, 100:0.041 or 100: 0.075.
In the present invention, the solvent may be a solvent conventionally used in the art, and preferably a ketone solvent and/or an amide solvent. The ketone solvent may be acetone and/or butanone. The amide solvent may be dimethylformamide.
In the present invention, the amount of the solvent may be an amount conventionally used in the art, for example, the mass ratio of the sum of the solid epoxy resin and the liquid epoxy resin to the solvent is 100 (120-135), and further, for example, 100:120, 100:125, 100:130 or 100: 135.
When the solvent is a ketone solvent, the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the solvent is preferably 100 (30-45), such as 100:30, 100:35, 100:40 or 100: 45.
When the ketone solvent is butanone, the mass ratio of the mass sum of the solid epoxy resin and the liquid epoxy resin to the solvent is preferably 100 (20-30), such as 100:20, 100:25 or 100: 30.
When the ketone solvent is acetone, the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the solvent is preferably 100 (10-15), for example 100:10 or 100: 15.
When the solvent is an amide-based solvent, the mass ratio of the sum of the masses of the solid epoxy resin and the liquid epoxy resin to the solvent is preferably 100: 90.
In the present invention, the inorganic filler may be an inorganic filler that is conventional in the art, such as magnesia and/or alumina.
Wherein, the magnesium oxide is micron-sized powder, and the purity of the magnesium oxide is not less than 99.5%. The average particle size of the magnesium oxide is preferably 0.1 to 50 μm.
Wherein, the aluminum oxide is micron-sized powder generally, and the purity of the aluminum oxide is not less than 99.5 percent generally. The average grain size of the aluminum oxide is preferably 0.1-100 μm.
In the present invention, the amount of the inorganic filler may be an amount conventionally used in the art, for example, the mass ratio of "the sum of the masses of the solid epoxy resin and the liquid epoxy resin" to the inorganic filler is 100 (360-375), and further 100:375, 100:370, 100:365 or 100:360, for example.
When the inorganic filler is magnesium oxide, the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the inorganic filler is preferably 100 (10-40), such as 100:10, 100:20, 100:30 or 100: 40.
When the inorganic filler is aluminum oxide, the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the inorganic filler is preferably 100 (320-365), such as 100:365, 100:350, 100:335 or 100: 320.
The tetrapod-like zinc oxide whisker can be a tetrapod-like zinc oxide whisker which is conventional in the field, generally speaking, the tetrapod-like zinc oxide whisker has a white loose powder appearance and a three-dimensional tetrapod-like three-dimensional structure in a microcosmic sense, namely the whisker has a core, and four needle-like crystals are extended from the radial direction of the core, wherein each needle-like body is a monocrystal microfiber, the included angle of any two needle-like bodies is 109 degrees, the diameter of a central body of the whisker is 0.7-1.4 mu m, the diameter of the root of the needle-like body is 0.5-14 mu m, and the length of the needle-like body is 3-200 mu m.
Wherein the root diameter of the needle-shaped body is preferably 0.5 to 10 μm.
Wherein the length of the needle-shaped body is preferably 10-15 μm.
In the present invention, the mass ratio of the sum of the masses of the solid epoxy resin and the liquid epoxy resin to the tetrapod-like zinc oxide whiskers is preferably 100:5, 100:10, 100:15, or 100: 20.
In the invention, the bisphenol a polyether ester liquid crystal block epoxy resin polymer generally refers to a copolymer of polyether ester liquid crystal epoxy resin and bisphenol a type epoxy resin, and preferably, the epoxy value of the bisphenol a polyether ester liquid crystal block epoxy resin polymer is 0.21-0.24.
In the invention, the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the bisphenol A polyether ester liquid crystal block epoxy resin polymer is preferably 100 (3-5), for example 100: 4.
In the present invention, the molecular weight of the polycarboxylic acid polymer is preferably 3000 to 3400, for example 3200.
In the present invention, the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the polycarboxylic acid-based polymer is preferably 100 (0.3 to 0.4), for example, 100: 0.4.
In the present invention, the epoxy resin composition may further comprise a coupling agent, such as a silane coupling agent, and further such as an epoxy silane coupling agent KH-560.
The amount of the coupling agent can be an amount conventionally used in the art, for example, the amount of the coupling agent is 1 to 2% of the mass of the inorganic filler, and further for example, 2%.
In a preferred embodiment of the present invention, the epoxy resin composition comprises the following components in parts by weight: 20-80 parts of solid epoxy resin, 20-80 parts of liquid epoxy resin, 5-15 parts of toughening agent, 15-30 parts of curing agent, 0.01-0.1 part of curing accelerator, 10-430 parts of inorganic filler, 10-185 parts of solvent, 5-20 parts of tetrapod-like zinc oxide whisker, 3-6 parts of bisphenol A polyether ester liquid crystal block epoxy resin polymer and 0.3-0.5 part of polycarboxylic acid polymer.
In a preferred embodiment of the present invention, the epoxy resin composition comprises the following components in parts by weight: 20-80 parts of solid epoxy resin, 20-80 parts of liquid epoxy resin, 5-15 parts of toughening agent, 15-30 parts of curing agent, 0.01-0.1 part of curing accelerator, 10-430 parts of inorganic filler, 10-185 parts of solvent, 1-10 parts of coupling agent, 5-20 parts of tetrapod-like zinc oxide whisker, 3-6 parts of bisphenol A polyether ester liquid crystal block epoxy resin polymer and 0.3-0.5 part of polycarboxylic acid polymer.
In a preferred embodiment of the present invention, the epoxy resin composition comprises the following components in parts by weight: 20-80 parts of bisphenol A glycidyl ether epoxy resin, 20-80 parts of bisphenol A epoxy resin with the average molecular weight of 300-500, 5-15 parts of random carboxyl nitrile rubber, 15-30 parts of diaminodiphenyl sulfone, 0.01-0.1 part of 2-ethyl-4-methylimidazole, 10-30 parts of magnesium oxide, 300-400 parts of aluminum oxide, 80-110 parts of dimethylformamide, 15-75 parts of butanone, 10-50 parts of acetone, 1-10 parts of epoxy silane coupling agent KH-560, 5-20 parts of tetrapod-like zinc oxide whiskers, 3-6 parts of bisphenol A polyether ester liquid crystal block epoxy resin polymer and 0.3-0.5 part of polycarboxylic acid polymer.
In a preferred embodiment of the present invention, the epoxy resin composition comprises the following components in parts by weight: 20 parts of bisphenol A glycidyl ether epoxy resin, 80 parts of bisphenol A epoxy resin with the average molecular weight of 300-500, 5 parts of random carboxyl nitrile rubber, 28 parts of diaminodiphenyl sulfone, 0.025 part of 2-ethyl-4-methylimidazole, 10 parts of magnesium oxide, 365 parts of aluminum oxide, 90 parts of dimethylformamide, 20 parts of butanone, 10 parts of acetone, 7.6 parts of epoxy silane coupling agent KH-560, 5 parts of the tetrapod-like zinc oxide whisker, 4 parts of the bisphenol A polyether ester liquid crystal block epoxy resin polymer and 0.4 part of the polycarboxylic acid polymer.
In a preferred embodiment of the present invention, the epoxy resin composition comprises the following components in parts by weight: 40 parts of bisphenol A glycidyl ether epoxy resin, 60 parts of bisphenol A epoxy resin with the average molecular weight of 300-500, 8 parts of random carboxylated nitrile rubber, 24 parts of diaminodiphenyl sulfone, 0.030 part of 2-ethyl-4-methylimidazole, 20 parts of magnesium oxide, 350 parts of aluminum oxide, 90 parts of dimethylformamide, 25 parts of butanone, 10 parts of acetone, 7.6 parts of epoxy silane coupling agent KH-560, 10 parts of the tetrapod-like zinc oxide whisker, 4 parts of the bisphenol A polyether ester liquid crystal block epoxy resin polymer and 0.4 part of the polycarboxylic acid polymer.
In a preferred embodiment of the present invention, the epoxy resin composition comprises the following components in parts by weight: 60 parts of bisphenol A glycidyl ether epoxy resin, 40 parts of bisphenol A epoxy resin with the average molecular weight of 300-500, 11 parts of random carboxylated nitrile rubber, 21 parts of diaminodiphenyl sulfone, 0.041 part of 2-ethyl-4-methylimidazole, 20 parts of magnesium oxide, 335 parts of aluminum oxide, 90 parts of dimethylformamide, 25 parts of butanone, 15 parts of acetone, 7.6 parts of epoxy silane coupling agent KH-560, 15 parts of the tetrapod-like zinc oxide whisker, 4 parts of the bisphenol A polyether ester liquid crystal block epoxy resin polymer and 0.4 part of the polycarboxylic acid polymer.
In a preferred embodiment of the present invention, the epoxy resin composition comprises the following components in parts by weight: 80 parts of bisphenol A glycidyl ether epoxy resin, 20 parts of bisphenol A epoxy resin with the average molecular weight of 300-500, 14 parts of random carboxyl nitrile rubber, 18 parts of diaminodiphenyl sulfone, 0.075 part of 2-ethyl-4-methylimidazole, 40 parts of magnesium oxide, 320 parts of aluminum oxide, 90 parts of dimethylformamide, 30 parts of butanone, 15 parts of acetone, 7.6 parts of epoxy silane coupling agent KH-560, 20 parts of the tetrapod-like zinc oxide whisker, 4 parts of the bisphenol A polyether ester liquid crystal block epoxy resin polymer and 0.4 part of the polycarboxylic acid polymer.
The invention also provides a preparation method of the epoxy resin composition, which comprises the following steps:
mixing the mixture A, the solid epoxy resin, the liquid epoxy resin, the toughening agent, the curing accelerator, the bisphenol A polyether ester liquid crystal block epoxy resin polymer, the polycarboxylic acid polymer, the tetrapod-like zinc oxide whiskers and the inorganic filler; the mixture A is prepared by mixing the solvent and the curing agent;
when the epoxy resin composition further comprises the coupling agent, the mixture a, the solid epoxy resin, the liquid epoxy resin, the toughening agent, the curing accelerator, the bisphenol a polyether ester liquid crystal block epoxy resin polymer, the polycarboxylic acid polymer, the tetrapod-like zinc oxide whiskers, the inorganic filler and the coupling agent are mixed.
When a plurality of solvent types are used as the solvent, all the solvents are mixed in advance and then used, and the mixing is based on uniform mixing according to the common knowledge in the field.
In the present invention, it is preferable that the solid epoxy resin, the liquid epoxy resin, the toughening agent, the bisphenol a polyetherester liquid crystal block epoxy resin polymer, the polycarboxylic acid-based polymer, the curing accelerator, the tetrapod-like zinc oxide whiskers, and the inorganic filler be added to the mixture a in this order.
In the invention, the mixing can be carried out according to the conventional process conditions in the field, for example, the shear stirring is carried out for 5-10 min under the condition of 4000-6000 rpm (for example, 5000rpm) in a high-shear mixing emulsifier; then, for example, the mixture is first sheared and stirred at 900-2000 rpm (e.g., 1200rpm) for 30-60 min, and then stirred at 90-150 rpm for 10-30 h.
The invention also provides an application of the epoxy resin composition as a binder.
The invention also provides an aluminum-based copper-clad plate, which has the following structure: the structure I is as follows: the aluminum-based copper-clad plate sequentially comprises a copper foil layer, a glue layer and an aluminum plate layer which are mutually overlapped; the glue layer is prepared from the epoxy resin composition;
or, structure two: the aluminum-based copper-clad plate sequentially comprises a first copper foil layer, a first glue solution layer, an aluminum plate layer, a second glue solution layer and a second copper foil layer which are mutually overlapped, and the first glue solution layer and the second glue solution layer are both prepared from the epoxy resin composition.
The invention also provides a preparation method of the aluminum-based copper-clad plate, which comprises the following steps:
when the aluminum-based copper-clad plate is in a structural formula I: coating the epoxy resin composition on the surface of one side of a copper foil, drying, and then attaching and hot-pressing one side of an aluminum plate and the gluing surface of the copper foil to obtain the epoxy resin composition;
when the aluminum-based copper-clad plate is of a second structure: and coating the epoxy resin composition on the surface of one side of the copper foil, drying, respectively attaching the two sides of an aluminum plate to the gluing surfaces of the copper foil, and carrying out hot pressing to obtain the aluminum-clad plate.
The copper foil generally refers to a copper foil material which is conventionally used for manufacturing copper clad laminates and printed circuit boards in the field, such as electrolytic copper foil.
Wherein, preferably, the coating equipment is a glue spreader.
Wherein the drying temperature is preferably 150-200 ℃.
Wherein the drying time is preferably 3-7 min.
Wherein after the drying, the thickness of the epoxy resin composition can be 60-150 μm.
Wherein, preferably, before the attaching, the aluminum plate is subjected to surface degreasing and/or oxidation treatment.
Wherein, preferably, the hot-pressing device is a vacuum hot press.
Wherein, preferably, the hot pressing conditions are as follows: at 60-210 ℃ and 6-80 kgf/cm2And hot pressing for 2-3 h under the pressure and the vacuum degree of 10 mmHg.
Wherein, preferably, the hot pressing is carried out, and then the hot pressing is cooled to 60 ℃ and then taken out.
Wherein, aluminum plate can be one side with the glue coating face laminating of copper foil, also can be both sides respectively with the glue coating face laminating of copper foil.
And when the two sides of the aluminum plate are respectively attached to the gluing surfaces of the copper foil, the double-sided aluminum-based copper-clad plate is obtained.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) the epoxy resin composition has high heat resistance, excellent heat conductivity and electric insulation.
(2) The double-sided aluminum-based copper-clad plate prepared from the epoxy resin composition has good heat resistance, remarkably improves the heat conduction performance (the highest heat conduction coefficient can reach 2.3W/m.K) and the electric insulation performance (the breakdown voltage can reach 5.8KV), effectively ensures the safety of LED products and prolongs the service life.
Drawings
FIG. 1 is a schematic structural diagram of a double-sided aluminum-based copper-clad plate prepared in the embodiment.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples:
the epoxy resin A is bisphenol A glycidyl ether epoxy resin, the manufacturer is south Asia, and the model is NPES-901 (the epoxy value is between 0.20 and 0.25);
the epoxy resin B is bisphenol A low-molecular epoxy resin, the manufacturer is Changchun chemical industry, and the model is BE188 (the epoxy value is between 0.40 and 0.55);
the toughening agent is random carboxyl nitrile rubber, the manufacturer is Rui Weng, the model is 1072CGX (the number average molecular weight is 27500)
The curing agent is diamino diphenyl sulfone, and the manufacturer is tiger biochemical engineering, and the purity is not less than 99.3%;
the curing accelerator is 2-ethyl-4-methylimidazole, the manufacturer is a four-country chemical product, and the purity is chemical purity;
the magnesium oxide manufacturer is a Hilimron, the model is HG204-Q-D-2, the purity is not less than 99.5%, and the average grain diameter is 0.1-50 mu m;
the alumina manufacturer is Sumitomo chemistry, the model is AM-21, the purity is not less than 99.5%, and the average grain diameter is 0.1-100 mu m;
the tetrapod-like zinc oxide whisker manufacturer is a crystal science and technology, is AT-01 in type, has the purity of not less than 99 percent, has the needle body length of 10-50 mu m and has the needle body root diameter of 0.5-10 mu m;
a bisphenol A polyether ester liquid crystal block epoxy resin polymer manufacturer is a new material with the model of SGE4816 (the epoxy value is between 0.21 and 0.24);
the polycarboxylic acid polymer manufacturer is a new material with the model of SGR-003 (the number average molecular weight is 3200)
The silane coupling agent is epoxy silane coupling agent KH-560, and the manufacturer is boiling point chemical industry;
the calcium carbonate whisker manufacturer is a Geranium technology with the model of NP-CW 2;
the manufacturer of the polyether modified polydimethylsiloxane BYK-346 is German Bike;
BYK-W969 from BYK;
dimethylformamide, butanone and acetone are all industrial grade.
TABLE 1-1 raw materials and proportions (in parts by mass) of epoxy resin glue
TABLE 1-2 raw materials and proportions (in parts by mass) of epoxy resin glue
(1) The preparation method of the epoxy resin glue solution comprises the following steps:
the raw materials shown in the tables 1-1 and 1-2 are mixed according to the following method:
adding dimethylformamide, butanone and acetone into a dissolving kettle, adding diaminodiphenyl sulfone under stirring, and stirring for about 30-60 minutes until the solution is uniform and transparent;
secondly, adding other raw materials into the solution in the first step according to the mass ratio shown in the table 1, mixing, and stirring for 5-10 min at the rotating speed of 5000rpm by using a high-shear mixing emulsifying machine to obtain the epoxy resin glue solution.
The epoxy resin glue solution systems prepared in the embodiments 1 to 4 are uniformly dispersed and have no agglomeration and sedimentation.
(2) The preparation method of the double-sided aluminum-based copper-clad plate comprises the following steps:
preparing a glue-coated copper foil: and (3) respectively taking the epoxy resin glue solutions prepared in the examples 1-4 and the comparative examples 1-13, uniformly coating the epoxy resin glue solutions on the rough surface of the electrolytic copper foil, and horizontally putting the electrolytic copper foil into an oven for baking. Controlling the temperature of the oven at 150-200 ℃ and controlling the baking time at 3-7 minutes; the thickness of the adhesive layer is controlled to be 60-150 mu m.
Placing a prepared glue coated copper foil on each of two surfaces of the aluminum plate subjected to surface oil removal and oxidation treatment, and keeping the aluminum plate with the glue coated surface of the copper foil attached; putting the mixture into a vacuum hot press, and heating the mixture at a temperature of 60-210 ℃ and a kgf of 6-80 kgf/cm2And (3) hot pressing for 2-3 hours under the pressure and the vacuum degree of 10mmHg, cooling to 60 ℃, and taking out to obtain the double-sided aluminum-based copper-clad plate finished product.
FIG. 1 is a schematic structural diagram of a double-sided aluminum-based copper-clad plate prepared by the method. The double-sided aluminum-based copper-clad plate sequentially comprises the following components in a mutual superposition mode: a first copper foil layer 1, a first glue layer 2, an aluminum plate layer 3, a second glue layer 4 and a second copper foil layer 5.
Effect example 1
Respectively taking the double-sided aluminum-based copper-clad plates prepared from the epoxy resin glue solutions of the embodiments 1-4 and the comparative examples 1-13, and carrying out the following performance tests:
thickness: the detection method refers to the CPCA 4105-20106.2.4.2 nominal thickness and tolerance of the insulation bonding layer;
thermal stress: the test method refers to the thermal stress of IPC-TM-6502.4.13.1 laminates;
coefficient of thermal conductivity: the detection method refers to appendix A of CPCA 4105-;
breakdown voltage: the detection method refers to the breakdown voltage (vertical plate) of CPCA 4105-2010 C.8.
Specific data are shown in tables 2-1 and 2-2.
Table 2-1 comparison of performances of double-sided aluminum-based copper-clad plate prepared from glue solution of embodiment and comparative example
Table 2-2 comparison of performance of double-sided aluminum-based copper-clad plate prepared from glue solution of examples and comparative examples
Claims (52)
1. An epoxy resin composition, characterized in that it comprises the following components: solid epoxy resin, liquid epoxy resin, a toughening agent, a curing accelerator, an inorganic filler, a solvent, tetrapod-like zinc oxide whiskers, a bisphenol A polyether ester liquid crystal block epoxy resin polymer and a polycarboxylic acid polymer, wherein:
the bisphenol A polyether ester liquid crystal block epoxy resin polymer manufacturer is a new material with the model of SGE 4816;
the polycarboxylic acid polymer manufacturer is a new hucho material with the model of SGR-003;
the number average molecular weight of the polycarboxylic acid polymer is 2500-4000;
the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the tetrapod-like zinc oxide whisker is 100 (5-20);
the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the bisphenol A polyether ester liquid crystal block epoxy resin polymer is 100 (3-6);
the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the polycarboxylic acid polymer is 100 (0.3-0.5).
2. The epoxy resin composition of claim 1, wherein the solid epoxy resin is a bisphenol a glycidyl ether epoxy resin;
and/or the mass ratio of the solid epoxy resin to the liquid epoxy resin is (1:4) - (4: 1);
and/or the liquid epoxy resin is bisphenol A epoxy resin with the number average molecular weight of 300-500.
3. The epoxy resin composition according to claim 2, wherein the epoxy value of the bisphenol a glycidyl ether epoxy resin is 0.20 to 0.25.
4. The epoxy resin composition of claim 2, wherein the mass ratio of the solid epoxy resin to the liquid epoxy resin is 1:4, 2:3, 3:2, or 4: 1.
5. The epoxy resin composition according to claim 2, wherein the bisphenol A epoxy resin having a number average molecular weight of 300 to 500 has an epoxy value of 0.40 to 0.55.
6. The epoxy resin composition of claim 1, wherein the toughening agent is one or more of random carboxylated nitrile rubber, polyvinyl butyral, and phenoxy resin;
and/or the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the toughening agent is 100 (5-15);
and/or the curing agent is an aromatic amine curing agent;
and/or the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the curing agent is 100 (15-30);
and/or the curing accelerator is an imidazole curing accelerator;
and/or the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the mass of the curing accelerator is 100 (0.01-0.10);
and/or the solvent is a ketone solvent and/or an amide solvent;
and/or the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the solvent is 100 (120-135);
and/or the inorganic filler is magnesium oxide and/or aluminum oxide;
and/or the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the inorganic filler is 100 (360-375).
7. The epoxy resin composition of claim 6, wherein the toughening agent is a random carboxylated nitrile rubber.
8. The epoxy resin composition according to claim 7, wherein the random carboxylated nitrile rubber has a number average molecular weight of 20000 to 50000.
9. The epoxy resin composition according to claim 6, wherein the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the toughening agent is 100:5, 100:8, 100:11 or 100: 14.
10. The epoxy resin composition of claim 6, wherein the curing agent is diaminodiphenyl sulfone.
11. The epoxy resin composition according to claim 6, wherein the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the curing agent is 100:28, 100:24, 100:21 or 100: 18.
12. The epoxy resin composition according to claim 6, wherein the curing accelerator is 2-ethyl-4-methylimidazole.
13. The epoxy resin composition according to claim 6, wherein the mass ratio of the sum of the solid epoxy resin and the liquid epoxy resin to the curing accelerator is 100:0.025, 100:0.030, 100:0.041 or 100: 0.075.
14. The epoxy resin composition according to claim 6, wherein when the solvent is a ketone solvent, the ketone solvent is acetone and/or butanone.
15. The epoxy resin composition according to claim 6, wherein when the solvent is an amide-based solvent, the amide-based solvent is dimethylformamide.
16. The epoxy resin composition according to claim 6, wherein the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the solvent is 100:120, 100:125, 100:130 or 100: 135.
17. The epoxy resin composition according to claim 6, wherein when the inorganic filler is magnesium oxide, the magnesium oxide has an average particle diameter of 0.1 to 50 μm.
18. The epoxy resin composition according to claim 6, wherein when the inorganic filler is alumina, the alumina has an average particle diameter of 0.1 to 100 μm.
19. The epoxy resin composition according to claim 6, wherein the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the inorganic filler is 100:375, 100:370, 100:365 or 100: 360.
20. The epoxy resin composition according to claim 1, wherein the tetrapod-like zinc oxide whiskers have a needle root diameter of 0.5 to 14 μm and a needle length of 3 to 200 μm;
and/or the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the tetrapod-like zinc oxide whiskers is 100:5, 100:10, 100:15 or 100: 20;
and/or the epoxy value of the bisphenol A polyether ester liquid crystal block epoxy resin polymer is 0.21-0.24;
and/or the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the bisphenol A polyether ester liquid crystal block epoxy resin polymer is 100 (3-5);
and/or the molecular weight of the polycarboxylic acid polymer is 3000-3400;
and/or the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the polycarboxylic acid polymer is 100 (0.3-0.4).
21. The epoxy resin composition according to claim 20, wherein the tetrapod-like zinc oxide whiskers have a needle root diameter of 0.5 to 10 μm and a needle length of 10 to 15 μm.
22. The epoxy resin composition according to claim 20, wherein the mass ratio of the sum of the mass of the solid epoxy resin and the mass of the liquid epoxy resin to the bisphenol a polyetherester liquid crystal block epoxy resin polymer is 100: 4.
23. The epoxy resin composition according to claim 20, wherein the polycarboxylic acid-based polymer has a molecular weight of 3200.
24. The epoxy resin composition according to claim 20, wherein the mass ratio of the sum of the masses of the solid epoxy resin and the liquid epoxy resin to the polycarboxylic acid-based polymer is 100: 0.4.
25. The epoxy resin composition according to any one of claims 1 to 24, further comprising a coupling agent.
26. The epoxy resin composition of claim 25, wherein the coupling agent is a silane coupling agent.
27. The epoxy resin composition of claim 26, wherein the coupling agent is an epoxy silane coupling agent KH-560.
28. The epoxy resin composition according to claim 25, wherein the coupling agent is 1 to 2% by mass of the inorganic filler.
29. The epoxy resin composition of claim 28, wherein the coupling agent is 2% by mass of the inorganic filler.
30. A process for preparing an epoxy resin composition according to any one of claims 1 to 24, comprising the steps of:
mixing the mixture A, the solid epoxy resin, the liquid epoxy resin, the toughening agent, the curing accelerator, the bisphenol A polyether ester liquid crystal block epoxy resin polymer, the polycarboxylic acid polymer, the tetrapod-like zinc oxide whiskers and the inorganic filler; the mixture A is prepared by mixing the solvent and the curing agent.
31. The method of claim 30, wherein the solid epoxy resin, the liquid epoxy resin, the toughening agent, the bisphenol a polyetherester liquid crystal block epoxy polymer, the polycarboxylic acid-based polymer, the curing accelerator, the tetrapod-like zinc oxide whiskers, and the inorganic filler are added to the mixture a in this order.
32. The method of claim 31, wherein the mixing is performed by shearing and stirring at 4000-6000 rpm for 5-10 min in a high shear mixer-emulsifier.
33. The method of claim 32, wherein the mixing is performed by shearing and stirring at 5000rpm for 5-10 min in a high shear mixer-emulsifier.
34. The method of claim 31, wherein the mixing is performed by shearing and stirring at 900 to 2000rpm for 30 to 60min in a high shear mixer-emulsifier, and then stirring at 90 to 150rpm for 10 to 30 h.
35. The method of claim 34, wherein the mixing is performed by first shearing and stirring at 1200rpm for 30-60 min and then stirring at 90-150 rpm for 10-30 h.
36. A process for preparing an epoxy resin composition according to any one of claims 25 to 29, comprising the steps of:
when the epoxy resin composition further comprises the coupling agent, mixing the mixture A, the solid epoxy resin, the liquid epoxy resin, the toughening agent, the curing accelerator, the bisphenol A polyether ester liquid crystal block epoxy resin polymer, the polycarboxylic acid polymer, the tetrapod-like zinc oxide whiskers, the inorganic filler and the coupling agent; the mixture A is prepared by mixing the solvent and the curing agent.
37. The method of claim 36, wherein the solid epoxy resin, the liquid epoxy resin, the toughening agent, the bisphenol a polyetherester liquid crystal block epoxy polymer, the polycarboxylic acid-based polymer, the curing accelerator, the tetrapod-like zinc oxide whiskers, and the inorganic filler are added to the mixture a in this order.
38. The method of claim 37, wherein the mixing is performed by shearing and stirring at 4000-6000 rpm for 5-10 min in a high shear mixer-emulsifier.
39. The method of claim 38, wherein the mixing is shear stirring in a high shear mixer emulsifier at 5000rpm for 5-10 min.
40. The method of claim 37, wherein the mixing is performed by shearing and stirring at 900 to 2000rpm for 30 to 60min in a high shear mixer-emulsifier, and then stirring at 90 to 150rpm for 10 to 30 h.
41. The method for preparing the epoxy resin composition according to claim 40, wherein the mixing is performed by first shearing and stirring at 1200rpm for 30-60 min and then stirring at 90-150 rpm for 10-30 h.
42. Use of an epoxy resin composition according to any one of claims 1 to 29 as a binder.
43. An aluminum-based copper-clad plate is characterized in that the structure is as follows:
the structure I is as follows: the aluminum-based copper-clad plate sequentially comprises a copper foil layer, a glue layer and an aluminum plate layer which are mutually overlapped; the glue layer is prepared from the epoxy resin composition as defined in any one of claims 1 to 29;
or, structure two: the aluminum-based copper-clad plate sequentially comprises a first copper foil layer, a first glue solution layer, an aluminum plate layer, a second glue solution layer and a second copper foil layer which are mutually overlapped, wherein the first glue solution layer and the second glue solution layer are both prepared from the epoxy resin composition as defined in any one of claims 1-29.
44. The preparation method of the aluminum-based copper-clad plate according to claim 43, which is characterized by comprising the following steps:
when the aluminum-based copper-clad plate is in a first structure: coating the epoxy resin composition of any one of claims 1 to 29 on the surface of one side of a copper foil, drying, attaching one side of an aluminum plate to the adhesive-coated surface of the copper foil, and carrying out hot pressing;
when the aluminum-based copper-clad plate is of a second structure: coating the epoxy resin composition of any one of claims 1 to 29 on one side surface of a copper foil, drying, respectively attaching two sides of an aluminum plate to the adhesive-coated surfaces of the copper foil, and hot-pressing to obtain the aluminum-clad plate.
45. The method for preparing the aluminum-based copper-clad plate according to claim 44, wherein the copper foil is an electrolytic copper foil.
46. The method for preparing the aluminum-based copper-clad plate according to claim 44, wherein the coating equipment is a coater.
47. The method for preparing the aluminum-based copper-clad plate according to claim 44, wherein the drying temperature is 150-200 ℃.
48. The method for preparing the aluminum-based copper-clad plate according to claim 44, wherein the drying time is 3-7 min.
49. The method for preparing the aluminum-based copper-clad plate according to claim 44, wherein the aluminum plate is subjected to surface degreasing and/or oxidation treatment before the bonding.
50. The method for preparing the aluminum-based copper-clad plate according to claim 44, wherein the hot-pressing equipment is a vacuum hot-pressing machine.
51. The method for preparing the aluminum-based copper-clad plate according to claim 50, wherein the hot pressing conditions are as follows: at 60-210 ℃ and 6-80 kgf/cm2And hot pressing for 2-3 h under the pressure and the vacuum degree of 10 mmHg.
52. The method for preparing the aluminum-based copper-clad plate according to claim 44, wherein the aluminum-based copper-clad plate is taken out after being cooled to 60 ℃ after being hot-pressed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910376566.7A CN110066494B (en) | 2019-05-07 | 2019-05-07 | Epoxy resin composition, preparation method and application thereof, and aluminum-based copper-clad plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910376566.7A CN110066494B (en) | 2019-05-07 | 2019-05-07 | Epoxy resin composition, preparation method and application thereof, and aluminum-based copper-clad plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110066494A CN110066494A (en) | 2019-07-30 |
| CN110066494B true CN110066494B (en) | 2022-05-17 |
Family
ID=67370262
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910376566.7A Active CN110066494B (en) | 2019-05-07 | 2019-05-07 | Epoxy resin composition, preparation method and application thereof, and aluminum-based copper-clad plate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110066494B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087759B (en) * | 2019-11-27 | 2023-02-17 | 广东盈骅新材料科技有限公司 | Resin composition and use thereof |
| CN112662131B (en) * | 2020-12-22 | 2023-10-20 | 广东盈骅新材料科技有限公司 | Liquid crystal modified resin composition, composite resin, prepreg and printed wiring board |
| CN116410568B (en) * | 2021-12-31 | 2025-07-18 | 广东生益科技股份有限公司 | A resin composition and a covering film prepared therefrom |
| CN114561087A (en) * | 2022-02-23 | 2022-05-31 | 江门市华锐铝基板股份公司 | Insulating glue solution for aluminum-based copper-clad plate |
| CN115353845B (en) * | 2022-08-26 | 2024-02-02 | 江西省航宇电子材料有限公司 | Stainless steel-based copper-clad plate silk-screen insulating adhesive and silk-screen printing method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006052730A1 (en) * | 2004-11-10 | 2006-05-18 | Dow Global Technologies Inc. | Amphiphilic block copolymer-toughened epoxy resins and powder coatings made therefrom |
| CN103694644A (en) * | 2013-12-30 | 2014-04-02 | 景旺电子科技(龙川)有限公司 | Epoxy resin composition, metal-based copper-clad plate and manufacturing method thereof |
| CN109181234A (en) * | 2018-08-09 | 2019-01-11 | 陕西生益科技有限公司 | A kind of high thermal conductivity high tenacity resin combination and its application |
-
2019
- 2019-05-07 CN CN201910376566.7A patent/CN110066494B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006052730A1 (en) * | 2004-11-10 | 2006-05-18 | Dow Global Technologies Inc. | Amphiphilic block copolymer-toughened epoxy resins and powder coatings made therefrom |
| CN103694644A (en) * | 2013-12-30 | 2014-04-02 | 景旺电子科技(龙川)有限公司 | Epoxy resin composition, metal-based copper-clad plate and manufacturing method thereof |
| CN109181234A (en) * | 2018-08-09 | 2019-01-11 | 陕西生益科技有限公司 | A kind of high thermal conductivity high tenacity resin combination and its application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110066494A (en) | 2019-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110066494B (en) | Epoxy resin composition, preparation method and application thereof, and aluminum-based copper-clad plate | |
| WO2016090859A1 (en) | Thermosetting resin composition for degradable heat-conducting aluminum-based copper-clad plate, heat-conducting aluminum-based copper-clad plate, and preparation method and recovery method thereof | |
| CN101848604A (en) | Preparation method of CEM-3 copper clad plate with high heat conductivity | |
| TWI410188B (en) | Metal-base circuit substrate and method for manufacturing the same | |
| KR20110119256A (en) | Resin composition for heat conductive heat dissipation sheet, heat dissipation sheet and copper foil laminated plate using same | |
| CN102746798B (en) | High-heat-conductivity semi-cured glue film and preparation method of high-heat-conductivity semi-cured glue film | |
| CN101033327A (en) | Resin composition, prepreg using same, copper clad laminate for printed circuit, and printed circuit board | |
| CN1239654C (en) | A thermosetting adhesive film, and an adhesive structure based on the use thereof | |
| WO2015056555A1 (en) | Metal substrate, metal-based circuit board, electronic device, and method for manufacturing metal-based circuit board | |
| CN108795354A (en) | A kind of heat conduction modified epoxide resin adhesive and preparation method | |
| CN104610707A (en) | Metal-base copper clad laminate manufactured through high-performance RCC (resin coated copper foil) and applied to high-power LED | |
| KR101704793B1 (en) | Printed circuit boards using the epoxy resin composition and its manufacturing method | |
| CN107429067B (en) | Laminate for insulation | |
| CN109181234A (en) | A kind of high thermal conductivity high tenacity resin combination and its application | |
| KR20180055014A (en) | Graphite sheet having excellent plane thermal conduction for heat radiation solution, Heat radiation solution containing the same and Manufacturing method thereof | |
| CN109265920A (en) | A kind of highly thermal-conductive resin composition and its application | |
| CN102469685A (en) | Heat-conducting double-sided rigid-flexible substrate and manufacturing method thereof | |
| CN112694719A (en) | Resin composition, preparation method thereof and metal substrate | |
| CN116406090B (en) | Production process of aluminum-based copper-clad aluminum foil plate | |
| CN109135652A (en) | A kind of high thermal conductivity toughened resin composition and its application | |
| CN110862653B (en) | Halogen-free resin composition, RCC, adhesive film and metal foil-clad laminate | |
| KR101074824B1 (en) | Print Circuit Board Having Excellent Heat Dissipating and Heat Spread and Light Emitting Diode Module Using Thereof | |
| WO2022176448A1 (en) | Thermosetting resin composition, susbstrate for power modules, and power module | |
| CN115109387B (en) | Resin composition and application thereof | |
| CN119110558B (en) | A heat dissipation graphite material for LED large-screen display and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |