CN110835456A - Epoxy resin composition and application thereof - Google Patents
Epoxy resin composition and application thereof Download PDFInfo
- Publication number
- CN110835456A CN110835456A CN201911232098.2A CN201911232098A CN110835456A CN 110835456 A CN110835456 A CN 110835456A CN 201911232098 A CN201911232098 A CN 201911232098A CN 110835456 A CN110835456 A CN 110835456A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- resin composition
- parts
- fiber
- prepreg
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/036—Multilayers with layers of different types
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2497/00—Characterised by the use of lignin-containing materials
- C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- 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
- C08K2003/2224—Magnesium hydroxide
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
The application discloses an epoxy resin composition and application thereof, wherein the epoxy resin composition comprises a first resin composition, a second resin composition and a third resin composition, wherein the first resin composition comprises epoxy resin, a curing agent, an accelerant and first reinforcing fibers; the second resin composition includes an epoxy resin, a curing agent, an accelerator, a filler, and a second reinforcing fiber. In the process of preparing the prepreg and the copper-clad plate by using the resin composition, the resin composition and the reinforcing fibers are integrally formed, so that the process of impregnating the resin composition with the reinforcing fibers is avoided, and the problem of interlayer bonding force reduction caused by the fact that fillers cannot fully enter the interior of a reinforcing material and are accumulated between layers is solved.
Description
Technical Field
The application relates to the technical field of metal foil-clad laminates, in particular to an epoxy resin composition, and also relates to a semi-cured material, a laminate and a printed circuit board which are prepared from the epoxy resin composition.
Background
The traditional copper clad laminate (copper clad laminate for short) is formed by impregnating a reinforcing material with an epoxy resin composition to prepare a prepreg, laminating the prepreg by a plurality of sheets and covering copper foils on two surfaces or one surface of the prepreg by hot pressing, the reinforcing material and the epoxy resin composition in the traditional copper clad laminate are not designed synchronously, so that the space for impregnating the resin composition in the reinforcing material is limited because the reinforcing material is preformed, further, the design of components and dosage in the resin composition is greatly restricted, especially, the use restriction of a filler is maximum, and the filler is easy to block the surface of the reinforcing material by the increase of the dosage or the increase of the particle size, so that a plurality of interlayer defects are caused, and therefore, the defect needs to be improved.
Disclosure of Invention
The epoxy resin composition is used for manufacturing the copper-clad plate, and the epoxy resin composition is not needed to be used for impregnating a reinforcing material in the process of manufacturing the copper-clad plate, and the problem of interlayer interface caused by the fact that the resin composition cannot fully enter the reinforcing material due to the increase of the using amount of a filler or the increase of the particle size does not exist.
Another object of the present invention is to provide a prepreg manufactured by using the above epoxy resin composition, which has the advantages of large single weight range, strong adhesion, high filler filling rate, etc.
It is another object of the present invention to provide a copper clad laminate having high heat resistance, high inter-layer reliability, low water absorption, low shrinkage, high insulation, excellent alkali resistance, excellent arc resistance, excellent breakdown voltage resistance, and processability, which is produced using the above epoxy resin composition.
In order to achieve the above object, the present application provides an epoxy resin composition comprising a first resin composition, a second resin composition, and a third resin composition, wherein,
the first resin composition comprises epoxy resin, a curing agent, an accelerator and first reinforcing fibers;
the second resin composition includes an epoxy resin, a curing agent, an accelerator, a filler, and a second reinforcing fiber.
The third resin composition comprises epoxy resin, a curing agent and an accelerator.
Preferably, the components and the solid weight parts in the first resin composition are as follows: 100 parts of epoxy resin, 1-60 parts of curing agent, 0.1-5 parts of accelerant, 3200 parts of reinforcing fiber 200 and a proper amount of solvent;
the second resin composition comprises the following components in parts by weight: 100 parts of epoxy resin, 1-60 parts of curing agent, 0.1-5 parts of accelerator, 30-230 parts of reinforcing fiber, 20-950 parts of filler and a proper amount of solvent.
The third resin composition comprises the following components in parts by weight: 100 parts of epoxy resin, 1-60 parts of curing agent, 0.1-5 parts of accelerator and a proper amount of solvent.
The first resin composition, the second resin composition and the third resin composition have a gelation time of 80 to 300 seconds at 171 ℃.
The epoxy resin has an epoxy equivalent of 100-700 g/eq.
Preferably, the epoxy resin is selected from one or a combination of at least any two of phenol novolac epoxy resin, DCPD phenol novolac epoxy resin, BPA novolac epoxy resin, XYLOK novolac epoxy resin, trifunctional novolac epoxy resin, bisphenol a epoxy resin, silicone modified epoxy resin, phosphate modified epoxy resin, polyurethane modified epoxy resin, polybutadiene epoxy resin, brominated epoxy resin, DOPO modified epoxy resin, cyclotriphosphazene modified epoxy resin, diphenylphosphine oxide epoxy resin, triglycidyl isocyanurate epoxy resin, p-aminophenol epoxy resin, diaminodiphenylmethane epoxy resin, aliphatic epoxy resin, cycloaliphatic epoxy resin, bisphenol F epoxy resin, o-cresol epoxy resin.
Preferably, the curing agent is one or a combination of at least any two of dicyandiamide, modified dicyandiamide, phenol novolac, o-cresol novolac, biphenyl phenol formaldehyde and benzoxazine.
The reinforcing fiber is selected from one or a composition of at least any two of glass fiber, carbon fiber, boron fiber, alumina fiber, basalt fiber, wood pulp fiber, cotton pulp fiber, aramid fiber and ramie fiber.
Further, the first resin composition preferably has a fiber diameter of 3 to 50 micrometers and a fiber length of 2000 to 50000 micrometers; the second resin composition preferably has a fiber diameter of 3 to 50 micrometers and a fiber length of 1000 micrometers to 30000 micrometers.
The filler is preferably selected from one or a combination of at least any two of aluminium hydroxide, aluminium oxide, magnesium hydroxide, magnesium oxide, silica, calcium carbonate, aluminium nitride, boron nitride, calcium nitride, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, mica, boehmite, talc powder or kaolin; the particle size distribution of the filler is 1-50 microns.
The accelerator is preferably one or a combination of at least any two selected from 2-methylimidazole, 1-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole and 2-phenyl-4-methylimidazole.
The solvent is a solvent capable of dissolving the epoxy resin and other components in the resin composition, such as one or a combination of at least any two of acetone, methanol, ethanol, toluene, xylene and DMF.
The addition amount of the solvent is determined according to the solid content of the epoxy resin composition; the solid contents of the first resin composition, the second resin composition and the third resin composition are all 50-80%.
The prepreg prepared by adopting the resin composition can be completed by three steps, namely: the primary prepreg, the secondary prepreg, and the final prepreg are sequentially completed, and the above three steps will be described in detail below.
The preparation process of the primary prepreg comprises the following steps: an appropriate amount of the first resin composition was poured into a press vulcanizer to prepare a primary prepreg.
In the application, the preparation of the primary prepreg by pouring a proper amount of the first resin composition into a flat vulcanizing machine specifically comprises controlling the initial temperature of the flat vulcanizing machine to be 20-80 ℃ above the softening point temperature of the thermosetting resin, so that the first resin composition is in a high-temperature flowing state with the viscosity of 100mPa & s or below, and then controlling the pressing temperature to be 130-200 ℃ and the pressure to be 10-70kg/cm2Pressing to form a primary prepreg is started. In the application, the thickness of the prepared primary prepreg is 0.1-1.5mm, and the single weight is 50-2100g/m2The fluidity is 2% -15%, and the volatile matter is less than or equal to 5%.
The preparation process of the secondary prepreg comprises the following steps: an appropriate amount of the second resin composition was poured into a press vulcanizer, the prepared primary prepreg was placed on the second resin composition, and then an appropriate amount of the second resin composition was poured on top of the primary prepreg to obtain a secondary prepreg.
In the application, the second resin composition and the primary prepreg are used for preparing the secondary prepreg, and the method specifically comprises the steps of firstly controlling the initial temperature of a flat vulcanizing machine to be 20-110 ℃ above the softening point temperature of the thermosetting resin, and then pouring the second resin composition into a mould of the flat vulcanizing machine to enable the resin composition to be in a high-temperature flowing state, wherein the viscosity of the resin composition is below 100mPa & s; laying the high-temperature flowing state second resin composition and the primary prepreg in a vulcanizing press to form a laying structure of a lower layer high-temperature flowing state second resin composition, a middle layer primary prepreg and an upper layer high-temperature flowing state second resin composition, wherein the lower layer high-temperature flowing state second resin composition and the upper layer high-temperature flowing state second resin composition are used in the same amount; then the pressing temperature of the plate vulcanizing machine is controlled to be 140 ℃ and 220 ℃, and the pressure is 10-90kg/cm2And pressing is started to press the secondary prepreg. The thickness of the prepared secondary prepreg is 0.2-2.8 mm, and the single weight is 150-2The fluidity is 7-30%, and the volatile matter is less than or equal to 5%.
And finally, a prepreg preparation process: preparing a final prepreg, namely a prepreg, by using the third resin composition and a secondary prepreg, specifically including coating the third resin composition on both surfaces of the secondary prepreg; and semi-curing the secondary prepreg coated with the third resin composition in an oven to obtain the prepreg.
In the application, the third resin composition and the secondary prepreg are used for preparing the prepreg, and the preparation method specifically comprises the steps of coating the third resin composition on two surfaces of the secondary prepreg in a spraying, rolling or brushing way, wherein the coating amount of the two surfaces is the same; and semi-curing the secondary prepreg coated with the third resin composition in an oven, wherein the oven temperature is 130-240 ℃. In the application, the thickness of the prepared prepreg is 0.3-3.2 mm, and the single weight is 200-2The fluidity is 2-24%, and the volatile matter is less than or equal to 3%. In addition, the application also provides a copper clad laminate prepared by using the epoxy resin composition, which comprises a laminate and copper foils pressed on one side or two sides of the laminate. The laminated board is formed by singly laminating a plurality of final prepregs or mixing a plurality of prepregs prepared by a traditional dipping method for a copper clad laminated board, laminating and hot-pressing, so that the laminated board contains at least one final prepreg. The preparation method of the metal foil clad laminate by using the prepreg specifically comprises the steps of singly laminating a plurality of prepregs or mixing and laminating a plurality of prepregs prepared by using the traditional dipping method for the metal foil clad laminate, arranging copper foils on one side or two sides of the laminated prepregs, and carrying out hot pressing to obtain the metal foil clad laminate, wherein the temperature of a pressing plate is 155-220 ℃, and the pressure is 30-60 Kg/cm2Then, the metal foil-clad laminate of 0.8 to 3.0mm is produced by hot pressing.
The beneficial effect of this application:
1. the epoxy resin composition and the reinforcing fibers are not separately designed but integrally formed, so that the process of impregnating the fibers with the resin composition does not exist, and the problem of interlayer bonding force reduction caused by stacking of the fillers among layers does not exist, so that the type and the dosage of the fillers can be designed at will according to performance requirements.
2. The copper-clad plate manufactured by using the resin composition has high heat resistance, high interlayer reliability, low water absorption, low shrinkage, high insulativity, excellent alkali resistance, arc resistance, breakdown voltage resistance and processability.
3. The prepreg in the application can also be randomly overlapped with the traditional prepreg, so that the performance of improving the traditional copper-clad plate by using the prepreg in the application is not enough.
4. The reinforcing fiber in the application can be any one or the combination of at least two fibers, the diversification of the fibers in the board is increased, and design conditions are created for improving the product performance by the composition of different fibers and exerting the advantages of various fibers.
Detailed Description
For the purpose of making the purpose, technical solutions and advantages of the present application more apparent, the present application is described in further detail with reference to the following embodiments, and it should be understood that the specific embodiments are only used for explaining the present application and are not used for limiting the present application.
In order to achieve the above object, the present application provides an epoxy resin composition including a first resin composition, a second resin composition, and a third resin composition. The first resin composition comprises the following components in parts by weight: 100 parts of epoxy resin, 1-60 parts of curing agent, 0.1-5 parts of accelerant, 3200 parts of reinforcing fiber 200-. The second resin composition comprises the following components in parts by weight: 100 parts of epoxy resin, 1-60 parts of curing agent, 0.1-5 parts of accelerator, 30-230 parts of reinforcing fiber, 20-950 parts of filler and a proper amount of solvent. The third resin composition comprises the following components in parts by weight: 100 parts of epoxy resin, 1-60 parts of curing agent, 0.1-5 parts of accelerator and a proper amount of solvent.
In the present application, the first resin composition, the second resin composition and the third resin composition have a gelation time of 80 to 300 seconds at 171 ℃.
In the present application, the epoxy equivalent of the epoxy resin is 100-700 g/eq.
The epoxy resin is selected from one or a combination of at least any two of phenol novolac epoxy resin, DCPD phenol novolac epoxy resin, BPA novolac epoxy resin, XYLOK novolac epoxy resin, trifunctional novolac epoxy resin, bisphenol A epoxy resin, silicone modified epoxy resin, phosphate modified epoxy resin, polyurethane modified epoxy resin, polybutadiene epoxy resin, brominated epoxy resin, DOPO modified epoxy resin, cyclotriphosphazene modified epoxy resin, diphenylphosphine oxide epoxy resin, triglycidyl isocyanurate epoxy resin, p-aminophenol epoxy resin, diaminodiphenylmethane epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, bisphenol F epoxy resin and o-cresol epoxy resin.
In the application, the curing agent is one or a combination of at least any two of dicyandiamide, modified dicyandiamide, phenol novolac, o-cresol novolac, biphenyl phenol novolac, benzoxazine phosphorus-containing phenol novolac, DDM (4' diaminodiphenylmethane), DDS (4, 4-diaminodiphenylsulfone).
In the application, the first reinforcing fiber and the second reinforcing fiber are selected from one or a combination of at least any two of glass fiber, carbon fiber, boron fiber, alumina fiber, basalt fiber, wood pulp fiber, cotton pulp fiber, aramid fiber and ramie fiber.
In addition, the first resin composition preferably has a fiber diameter of 3 to 50 micrometers and a fiber length of 2000 to 50000 micrometers; the second resin composition preferably has a fiber diameter of 3 to 50 micrometers and a fiber length of 1000 micrometers to 30000 micrometers.
In the present application, the filler is preferably selected from one or a combination of at least any two of aluminum hydroxide, aluminum oxide, magnesium hydroxide, magnesium oxide, silica, calcium carbonate, aluminum nitride, boron nitride, calcium nitride, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, mica, boehmite, talc, or kaolin; the particle size distribution of the filler is 1-50 microns.
In the present application, the accelerator is preferably one or a combination of at least any two of 2-methylimidazole (2-MI), 1-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole and 2-phenyl-4-methylimidazole.
In the present application, the solvent is a solvent capable of dissolving the epoxy resin and other components in the resin composition, such as one or a combination of at least any two of acetone, methanol, ethanol, toluene, xylene, and DMF. The addition amount of the solvent is determined according to the solid content of the epoxy resin composition; the solid contents of the first resin composition, the second resin composition and the third resin composition are all 50-80%.
The application also provides a prepreg (also called as prepreg), a laminated board, a metal foil-clad laminated board and a circuit board which are prepared by adopting the epoxy resin composition.
The preparation process of the primary prepreg comprises the following steps: an appropriate amount of the first resin composition was poured into a press vulcanizer to prepare a primary prepreg.
In the application, the preparation of the primary prepreg by pouring a proper amount of the first resin composition into a flat vulcanizing machine specifically comprises controlling the initial temperature of the flat vulcanizing machine to be 20-80 ℃ above the softening point temperature of the thermosetting resin, so that the first resin composition is in a high-temperature flowing state with the viscosity of 100mPa & s or below, and then controlling the pressing temperature to be 130-200 ℃ and the pressure to be 10-70kg/cm2Pressing to form a primary prepreg is started. In the application, the thickness of the prepared primary prepreg is 0.1-1.5mm, and the single weight is 50-2100g/m2The fluidity is 2% -15%, and the volatile matter is less than or equal to 5%.
The preparation process of the secondary prepreg comprises the following steps: an appropriate amount of the second resin composition was poured into a press vulcanizer, the prepared primary prepreg was placed on the second resin composition, and then an appropriate amount of the second resin composition was poured on top of the primary prepreg to obtain a secondary prepreg.
In the application, the second resin composition and the primary prepreg are used for preparing the secondary prepreg, and the method specifically comprises the steps of firstly controlling the initial temperature of a flat vulcanizing machine to be 20-110 ℃ above the softening point temperature of the thermosetting resin, and then pouring the second resin composition into a mould of the flat vulcanizing machine to enable the resin composition to be in a high-temperature flowing state, wherein the viscosity of the resin composition is below 100mPa & s; laying the high-temperature flowing second resin composition and the primary prepreg in a vulcanizing pressForming a laying structure of a lower layer high-temperature flow state second resin composition, a middle layer primary prepreg and an upper layer high-temperature flow state second resin composition, wherein the lower layer high-temperature flow state second resin composition and the upper layer high-temperature flow state second resin composition are used in the same amount; then the pressing temperature of the plate vulcanizing machine is controlled to be 140 ℃ and 220 ℃, and the pressure is 10-90kg/cm2And pressing is started to press the secondary prepreg. In the example, the thickness of the prepared secondary prepreg is 0.2-2.8 mm, and the single weight is 150-2The fluidity is 7-30%, and the volatile matter is less than or equal to 5%.
And finally, a prepreg preparation process: preparing a final prepreg, namely a prepreg, by using the third resin composition and a secondary prepreg, specifically including coating the third resin composition on both surfaces of the secondary prepreg; and semi-curing the secondary prepreg coated with the third resin composition in an oven to obtain the prepreg.
In the application, the preparation of the prepreg by using the third resin composition and the secondary prepreg specifically comprises coating the third resin composition on two surfaces of the secondary prepreg in a spraying, rolling or brushing manner, wherein in the example, the coating amounts of the two surfaces are the same; and semi-curing the secondary prepreg coated with the third resin composition in an oven, wherein the oven temperature is 130-240 ℃. In the application, the thickness of the prepared prepreg is 0.3-3.2 mm, and the single weight is 200-2The fluidity is 2-24%, and the volatile matter is less than or equal to 3%.
The preparation method of the metal foil clad laminate by using the prepreg specifically comprises the steps of singly laminating a plurality of prepregs or mixing and laminating a plurality of prepregs prepared by using the traditional dipping method for the metal foil clad laminate, arranging copper foils on one side or two sides of the laminated prepregs, and carrying out hot pressing to obtain the metal foil clad laminate, wherein the temperature of a pressing plate is 155-220 ℃, and the pressure is 30-60 Kg/cm2Then, the metal foil-clad laminate of 0.8 to 3.0mm is produced by hot pressing.
The copper clad laminate prepared as described above was tested for thermal stress at 288 ℃, T260 thermal delamination time, bake at 240 ℃, peel strength, flexural strength, dimensional stability, breakdown voltage, alkali resistance, volume resistivity, arc resistance, punching property, water absorption, solder dip resistance after PCT 1 hour, and water absorption, as further illustrated and described in the following examples.
Please refer to examples 1-9 and comparative examples 1-4. The following examples are given in detail, but the scope of the present application is not limited thereto. The manufacturing methods of the copper clad laminates of examples 1 to 9 and comparative examples 4 to 9 were the techniques described in the present application; the copper clad laminate of comparative examples 1 to 3 was produced by a conventional method. The fabrics in examples 1 to 9 and comparative examples 1 to 3 are glass cloth-based fabrics manufactured by a conventional method, and specifically, the fabrics are S1141 glass cloth-based prepregs which are good-tech.
The test preparation process comprises the following steps:
design examples 1-9 and comparative examples 1-3, wherein the table 1 is a composition component table of the copper-clad plates of the examples 1-9, the table 2 is a content table of each component in the copper-clad plates of the examples 1-9, and the table 3 is a manufacturing technical parameter of the copper-clad plates of the examples 1-9. Table 4 is a component table of the copper-clad plates of comparative examples 1 to 3, Table 5 is a content table of each component in the copper-clad plates of comparative examples 1 to 3, and Table 6 is a manufacturing technical parameter of the copper-clad plates of comparative examples 1 to 3.
Table 1 composition component table of copper clad laminate of examples 1 to 9
Table 2 table of contents of components in copper clad laminates of examples 1 to 9
Table 3 manufacturing technical parameters of examples 1 to 9 copper-clad plate
Table 4 composition component table of comparative examples 1-3 copper-clad plate
| Composition of | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Epoxy resin | DOPO modified epoxy resin | Bisphenol A epoxy | Brominated epoxy |
| Curing agent | Benzoxazine(s) | Phenol-novolaks | Phenol-novolaks |
| Reinforcing material | Glass fiber paper | Wood pulp paper and glass fiber paper | Wood pulp paper |
| Filler material | Magnesium hydroxide | Boehmite (BO) | Boehmite (BO) |
| Accelerator | 2-MI | 2-MI | 2-MI |
Table 5 content table of each component in comparative examples 1-3 copper-clad plate
Table 6 comparative examples 1-3 copper-clad plate manufacturing technical parameters
And (3) carrying out performance test on the copper-clad plates of the embodiments 1-9 and the comparative examples 1-3, wherein the test comprises the following steps:
a: thermal stress at 288 ℃ was measured by IPC-TM-6502.4.13.1 method.
B: t260 thermal stratification time was determined according to IPC-TM-6502.4.24.1.
C: and (3) baking the board at 240 ℃, namely baking the copper clad laminate with copper foils on both sides of the board at 240 ℃, and recording corresponding time when bubbles are layered.
D: the peel strength was measured by IPC-TM-6502.4.8.
E: the flexural strength was measured by IPC-TM-6502.4.4 method.
F: dimensional stability, determined according to IPC-TM-6502.4.3.9.
G: the punching property was measured according to the method of GB/T4722-20177.5.
H: water absorption was measured by IPC-TM-6502.6.2.1 method.
I: the dip resistance and water absorption after PCT 1 hour were measured by IPC-TM-6502.6.16 method.
J: alkali resistance: measured according to the method of GB/T4722-20176.2.
K: volume resistivity: measured according to the method of GB/T4722-20178.3.
L: arc resistance: measured according to the method of GB/T4722-20178.6.
M: breakdown voltage: measured according to the method of GB/T4722-20178.1.
The test results of the above tests are shown in table 7 and table 8, where table 7 is a test result table of the performance test performed on the copper-clad plates of examples 1 to 9, and table 8 is a test result table of the performance test performed on the copper-clad plates of comparative examples 1 to 3.
Table 7 test result table for performance test of copper clad laminate of embodiments 1 to 9
Table 8 test result table for performance test of copper clad laminate of comparative examples 1-3
In conclusion, compared with the traditional copper clad laminate, the epoxy resin composition and the reinforcing fibers in the application are not separately designed but integrally formed, so that the process of impregnating the fibers with the resin composition is avoided, and the problem of interlayer bonding force reduction caused by stacked filler layers is also avoided.
The prepreg in this application can carry out arbitrary coincide with traditional prepreg, can improve the performance of traditional copper-clad plate not enough, and reinforcing fiber in this application can be for arbitrary one kind or two kind at least fibrous combination, has increased fibrous diversification in the panel, for the complex through different fibre, exerts the advantage of various fibre and improves product property and has created the design condition.
The above examples are not intended to limit the content of the composition of the present application, and any minor modifications, equivalent variations and modifications of the above examples according to the technical spirit or composition ingredients or contents of the present application are within the scope of the present application.
The above-described embodiments of the present application do not limit the scope of the present application.
Claims (10)
1. An epoxy resin composition comprising a first resin composition, a second resin composition and a third resin composition, wherein,
the first resin composition comprises epoxy resin, a curing agent, an accelerator and first reinforcing fibers;
the second resin composition comprises epoxy resin, a curing agent, an accelerator, a filler and second reinforcing fibers;
the third resin composition comprises epoxy resin, a curing agent and an accelerator.
2. The epoxy resin composition according to claim 1,
the first resin composition comprises the following components in parts by weight: 100 parts of epoxy resin, 1-60 parts of curing agent, 0.1-5 parts of accelerant, 3200 parts of first reinforcing fiber 200-;
the second resin composition comprises the following components in parts by weight: 100 parts of epoxy resin, 1-60 parts of curing agent, 0.1-5 parts of accelerator, 30-230 parts of second reinforcing fiber, 20-950 parts of filler and a proper amount of solvent;
the third resin composition comprises the following components in parts by weight: 100 parts of epoxy resin, 1-60 parts of curing agent, 0.1-5 parts of accelerator and a proper amount of solvent.
3. The epoxy resin composition according to claim 1 or 2, wherein the first resin composition, the second resin composition and the third resin composition have a gelation time of 80 to 300 seconds at 171 ℃.
4. The epoxy resin composition as claimed in claim 1 or 2, wherein the epoxy resin has an epoxy equivalent of 100-700 g/eq;
the epoxy resin is selected from one or a composition of at least any two of phenol novolac epoxy resin, DCPD phenol novolac epoxy resin, BPA novolac epoxy resin, XYLOK novolac epoxy resin, trifunctional novolac epoxy resin, bisphenol A epoxy resin, organosilicon modified epoxy resin, phosphate modified epoxy resin, polyurethane modified epoxy resin, polybutadiene epoxy resin, brominated epoxy resin, DOPO modified epoxy resin, cyclotriphosphazene modified epoxy resin, diphenylphosphine oxide epoxy resin, triglycidyl isocyanurate epoxy resin, p-aminophenol epoxy resin, diaminodiphenylmethane epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, bisphenol F epoxy resin and o-cresol epoxy resin.
5. The epoxy resin composition according to claim 1 or 2, wherein the first reinforcing fiber and the second reinforcing fiber are each one or a combination of at least any two of glass fiber, carbon fiber, boron fiber, alumina fiber, basalt fiber, wood pulp fiber, cotton pulp fiber, aramid fiber, and ramie fiber.
6. The epoxy resin composition according to claim 1 or 2, wherein the first reinforcing fiber has a diameter of 3 to 50 μm and a length of 2000 to 50000 μm; the diameter of the second reinforcing fiber is 3-50 mu m, and the length of the second reinforcing fiber is 1000-30000 mu m.
7. The epoxy resin composition according to claim 1 or 2, wherein the curing agent is one or a combination of at least any two of dicyandiamide, modified dicyandiamide, phenol novolac, o-cresol novolac, biphenyl phenol formaldehyde, benzoxazine, phosphorus-containing phenol formaldehyde, DDM, DDS.
8. The epoxy resin composition according to claim 1 or 2, wherein the accelerator is one or a combination of at least any two of 2-methylimidazole, 1-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, and 2-phenyl-4-methylimidazole.
9. The epoxy resin composition according to claim 1 or 2, wherein the filler comprises one or a combination of at least any two of aluminum hydroxide, aluminum oxide, magnesium hydroxide, magnesium oxide, silica, calcium carbonate, aluminum nitride, boron nitride, calcium nitride, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, mica, boehmite, talc, or kaolin, and has a particle size in the range of 1 to 50 μm.
10. A prepreg, a laminate, a metal foil-clad laminate and a circuit board prepared based on the epoxy resin composition according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911232098.2A CN110835456B (en) | 2019-12-05 | 2019-12-05 | Epoxy resin composition and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911232098.2A CN110835456B (en) | 2019-12-05 | 2019-12-05 | Epoxy resin composition and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110835456A true CN110835456A (en) | 2020-02-25 |
| CN110835456B CN110835456B (en) | 2022-06-24 |
Family
ID=69578157
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911232098.2A Active CN110835456B (en) | 2019-12-05 | 2019-12-05 | Epoxy resin composition and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110835456B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111748114A (en) * | 2020-05-14 | 2020-10-09 | 江阴市沪澄绝缘材料有限公司 | Epoxy glass cloth prepreg for oil gas exploitation bridge plug and production method thereof |
| CN113621230A (en) * | 2021-09-01 | 2021-11-09 | 广东华彩复合材料有限公司 | Epoxy resin composite material for high-transparency prepreg and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101746102A (en) * | 2008-12-18 | 2010-06-23 | 建滔化工集团有限公司 | Compound base copper-clad laminate and manufacturing method thereof |
| CN102197088A (en) * | 2008-10-29 | 2011-09-21 | 住友电木株式会社 | Resin composition, resin sheet, prepreg, laminate board, multilayer printed wiring board, and semiconductor device |
| CN106398110A (en) * | 2016-09-13 | 2017-02-15 | 抚州市龙兴电子材料有限公司 | Glue solution for copper-clad plate, composite based CEM-1 copper-clad plate, and preparation methods of glue solution and composite based CEM-1 copper-clad plate |
| CN107163274A (en) * | 2017-06-20 | 2017-09-15 | 苏州生益科技有限公司 | A kind of low flow prepreg |
| CN110027276A (en) * | 2019-04-15 | 2019-07-19 | 山东金宝电子股份有限公司 | A kind of high CTI, Halogen CEM-1 copper-clad plate preparation method |
-
2019
- 2019-12-05 CN CN201911232098.2A patent/CN110835456B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102197088A (en) * | 2008-10-29 | 2011-09-21 | 住友电木株式会社 | Resin composition, resin sheet, prepreg, laminate board, multilayer printed wiring board, and semiconductor device |
| CN101746102A (en) * | 2008-12-18 | 2010-06-23 | 建滔化工集团有限公司 | Compound base copper-clad laminate and manufacturing method thereof |
| CN106398110A (en) * | 2016-09-13 | 2017-02-15 | 抚州市龙兴电子材料有限公司 | Glue solution for copper-clad plate, composite based CEM-1 copper-clad plate, and preparation methods of glue solution and composite based CEM-1 copper-clad plate |
| CN107163274A (en) * | 2017-06-20 | 2017-09-15 | 苏州生益科技有限公司 | A kind of low flow prepreg |
| CN110027276A (en) * | 2019-04-15 | 2019-07-19 | 山东金宝电子股份有限公司 | A kind of high CTI, Halogen CEM-1 copper-clad plate preparation method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111748114A (en) * | 2020-05-14 | 2020-10-09 | 江阴市沪澄绝缘材料有限公司 | Epoxy glass cloth prepreg for oil gas exploitation bridge plug and production method thereof |
| CN111748114B (en) * | 2020-05-14 | 2022-04-12 | 江阴市沪澄绝缘材料有限公司 | Epoxy glass cloth prepreg for oil gas exploitation bridge plug and production method thereof |
| CN113621230A (en) * | 2021-09-01 | 2021-11-09 | 广东华彩复合材料有限公司 | Epoxy resin composite material for high-transparency prepreg and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110835456B (en) | 2022-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110835451B (en) | Thermosetting resin composition and application thereof | |
| CN101223015B (en) | Process for producing prepreg with carrier, thin-type double sided board, process for producing thin-type double sided board and process for producing multilayered printed wiring board | |
| KR101503005B1 (en) | Thermosetting resin composition and Prepreg and Metal Clad laminate using the same | |
| JP5039707B2 (en) | Epoxy resin composition for printed wiring board, resin composition varnish, prepreg, metal-clad laminate, printed wiring board, and multilayer printed wiring board | |
| CN110835456B (en) | Epoxy resin composition and application thereof | |
| CN103709718B (en) | A kind of compositions of thermosetting resin and application thereof | |
| JP6512521B2 (en) | Laminated board, metal-clad laminated board, printed wiring board, multilayer printed wiring board | |
| KR101044114B1 (en) | Resin composition for printed circuit board and printed circuit board using the same | |
| CN112831153A (en) | Epoxy resin composition and prepreg and laminated board prepared from same | |
| TWI764902B (en) | Resin composition for printed wiring board and resin sheet for printed wiring board using the same | |
| CN110903603B (en) | Resin composition and application thereof | |
| CN114605779B (en) | Thermosetting resin composition, prepreg comprising thermosetting resin composition, circuit substrate and printed circuit board | |
| CN110845751B (en) | Preparation method of prepreg and metal foil-clad laminated board | |
| CN111531983B (en) | High-heat-resistance low-dielectric copper-clad plate and preparation method thereof | |
| JP2015228390A (en) | Method for manufacturing substrate | |
| KR102136861B1 (en) | Thermosetting resin composition for semiconductor pakage and preprege using the same | |
| CN104017327B (en) | The resistance to combustion resin combination of phosphorus-nitrogen type halogen-free, prepreg and film, copper foil laminates and its printed circuit board (PCB) | |
| JP5384233B2 (en) | Resin composition for printed circuit board and printed circuit board using the same | |
| JP2007301916A (en) | Metal-clad laminated sheet and its manufacturing method | |
| WO2021206041A1 (en) | Resin composition, resin film material, printed wiring board, and method for producing printed wiring board | |
| JP6444801B2 (en) | Method for producing low thermal expansion substrate | |
| KR20120090199A (en) | Non-halogen varnish and a prepreg and a laminated substrate thereof | |
| CN114672165A (en) | Halogen-free flame-retardant resin composition, prepreg prepared from same and laminated board for printed circuit | |
| JP2015120890A (en) | Thermosetting resin composition | |
| JPH0732541A (en) | Manufacture of metal foiled laminate |
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 |