CN107771418B - High-toughness halogen-free CEM-3 copper-clad plate - Google Patents
High-toughness halogen-free CEM-3 copper-clad plate Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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Abstract
The invention discloses a high-toughness halogen-free CEM-3 copper-clad plate which is prepared by the following method: (1) overlapping and matching a plurality of sticking surface prepregs on two sides of a plurality of sandwich prepregs to obtain a core material, and then covering copper foil on one side or two sides of the core material to obtain a semi-finished plate; (2) carrying out hot pressing on the semi-finished plate to obtain the composite material; the glue solution for preparing the high-toughness halogen-free CEM-3 copper-clad plate used for the prepreg comprises the following components in parts by weight: 75-120 parts of phenolic epoxy resin, 300-450 parts of flame-retardant modified liquid halogen-free epoxy resin, 150-250 parts of flame-retardant modified solid halogen-free epoxy resin, 25-50 parts of curing agent, 0.10-0.30 part of curing accelerator and 100-200 parts of organic solvent. The high-toughness halogen-free CEM-3 copper-clad plate not only has good heat resistance and chemical resistance, but also can reduce the pollution to the environment.
Description
Technical Field
The invention particularly relates to a high-toughness halogen-free CEM-3 copper-clad plate.
Background
A Copper Clad Laminate (CCL) is a main material for manufacturing a Printed Circuit Board (PCB), and thus is also an indispensable basic electronic material for the overall machines and components of any electronic products. With the rapid development of the PCB industry, the market demand of high-performance copper-clad laminates is increasing day by day, and the copper-clad laminates are developed in the green environmental protection era, and are becoming mature today, besides the heat resistance, TG value, CTE value and other properties of the products are concerned, the toughness, PCB processability and cohesiveness of the materials also become important points of attention, and the development of the balance of properties of the substrates of the copper-clad laminates becomes an important development trend for developing novel copper-clad laminates.
With the demand of light weight, thinness, shortness, smallness and digitalization of the present electronic products, miniaturization, multifunction, high performance and high reliability have become the mainstream development direction, so that the PCB is going to fine pattern, high density and high multilayering, and the requirements of the processes such as line width, line spacing, aperture, hole wall and the like in the production of the PCB industry are gradually moving towards high integration, high density,The development of high layers is in the direction. For example, mainstream high density interconnect laminates (HDI) require a microvia aperture of less than 6 mils, a microvia ring diameter of less than 0.35mm, and a contact density of 130in/m2The wiring density was l170in/m2In the above, the line width/line distance is less than 0.1mm/0.1mm, and the high-level HDI (more than twelve layers) needs to withstand the special processes such as high-level multiple hot pressing and the like and the more precise and detailed process requirements. With the development of high-density mounting technology, particularly the full-scale implementation of lead-free mounting and the rapid development of Surface Mount Technology (SMT), the times and temperature of repeated thermal shock of materials are higher than the conventional requirements in PCB processing and complete machine part mounting, and all of the requirements are finally transformed into the great challenge of high-performance copper-clad laminate reliability.
CEM-3(Composite Epoxy Material Grade-3) is a Composite copper clad laminate with performance level and price between CEM-1 and FR-4, and is prepared by using an Epoxy resin glass fiber cloth-based bonding sheet as a fabric, an Epoxy resin glass fiber felt-based bonding sheet core Material, covering a copper foil on one side or two sides, and then carrying out hot pressing. As the core material adopts the non-woven glass fiber felt as the reinforcing material, the mechanical strength of the CEM-3 is between FR-4 and the paper-based copper clad laminate (CEM-1), and the bending strength of the CEM-3 is slightly lower than that of FR-4 of a full glass fiber cloth structure. The epoxy resin is used for preparing CEM-3 as a formula of glue solution, and can improve the toughness of CEM-3. In order to improve the flame retardance of epoxy resin polymers, the flame retardant modification of the epoxy resin is mainly carried out by halogen, and the epoxy resin can cause environmental pollution and is not beneficial to environmental protection.
Disclosure of Invention
The invention aims to overcome the defects of low toughness, environmental pollution and the like of a CEM-3 copper-clad plate in the prior art, and provides glue solution for a high-toughness halogen-free CEM-3 copper-clad plate, a prepreg, the copper-clad plate and a preparation method thereof. The invention mainly adopts novolac epoxy resin with good heat resistance and excellent thermal conductivity to increase the toughness of the board, and selects a composite curing system to prepare the high-toughness halogen-free CEM-3 copper-clad plate. The product base material has good high toughness, heat resistance and heat conductivity, and the comprehensive performance is also excellent.
The invention solves the technical problems through the following technical scheme:
the invention provides a glue solution for a high-toughness halogen-free CEM-3 copper-clad plate, which comprises the following components in parts by weight: 75-120 parts of phenolic epoxy resin, 300-450 parts of flame-retardant modified liquid halogen-free epoxy resin, 150-250 parts of flame-retardant modified solid halogen-free epoxy resin, 25-50 parts of curing agent, 0.10-0.30 part of curing accelerator and 100-200 parts of organic solvent.
The flame-retardant modified liquid halogen-free epoxy resin and the flame-retardant modified solid halogen-free epoxy resin can adopt various conventionally used flame-retardant modified halogen-free epoxy resins in glue solution for copper clad plates in the field. The flame-retardant modified liquid halogen-free epoxy resin is preferably DOPO type liquid halogen-free flame-retardant epoxy resin. The flame-retardant modified solid halogen-free epoxy resin is preferably DOPO type solid halogen-free flame-retardant epoxy resin. The DOPO type liquid halogen-free flame-retardant epoxy resin preferably has the following performance indexes: an epoxy value of 320-. The DOPO type solid halogen-free flame-retardant epoxy resin has the following performance indexes: an epoxy value of 970-1070g/eg and a viscosity at 150 ℃ of 8000-11000 mPas. .
The curing agent may be one conventionally used in the art, and is preferably Dicyandiamide (DICY).
Among them, the curing accelerator may be one conventionally used in the art, and preferably is diphenylimidazole (2 PI).
Wherein the solvent is a solvent conventionally used in the art, preferably one or more of acetone, butanone, Dimethylformamide (DMF) and propylene glycol methyl ether. When the solvent is acetone, butanone, dimethylformamide and propylene glycol methyl ether, the weight ratio of acetone, butanone, dimethylformamide and propylene glycol methyl ether is preferably 1: 1: 6: 1.
the invention also provides a preparation method of the glue solution for the high-toughness halogen-free CEM-3 copper-clad plate, which comprises the following steps:
(1) mixing the curing agent, the curing accelerator and the solvent, and stirring until the curing agent, the curing accelerator and the solvent are dissolved to obtain a mixture A;
(2) mixing the mixture A with the halogen-free resin, and uniformly stirring to obtain a mixture B;
(3) and mixing the mixture B with the novolac epoxy resin under the stirring condition, shearing at the speed of 2200-2800 rpm, and curing to obtain the high-toughness halogen-free CEM-3 copper-clad plate glue solution.
In the preparation method of the glue solution for the high-toughness halogen-free CEM-3 copper-clad plate, all the raw material components are as described in the glue solution preparation component.
In step (1), the stirring method and conditions may be those conventional in the art. The stirring time is based on complete dissolution of the curing agent and the curing accelerator, and is preferably 3 to 5 hours. The rotation speed of the stirring is preferably 900 to 1400 rpm.
In step (2), the stirring method and conditions may be those conventional in the art. The stirring time is based on complete dissolution of the curing agent and the curing accelerator, and is preferably 3 to 5 hours. The rotation speed of the stirring is preferably 1000 to 1500 rpm.
In step (3), the method and conditions for the shearing may be those conventional in the art. The shearing time is preferably 1.0 to 2.0 hours. The rotation speed of the shearing is preferably 2300 to 2700rpm in the step (3), and the method and conditions for the aging can be conventional in the art. The curing is preferably carried out by stirring at a rotating speed of 1000-1600 rpm for 8-12 hours; more preferably 9 to 12 hours.
The invention also provides a preparation method of the prepreg for the high-toughness halogen-free CEM-3 copper-clad plate, which comprises the following steps: coating the glue solution for the high-toughness halogen-free CEM-3 copper-clad plate on a reinforcing material, and then drying to obtain the high-toughness halogen-free CEM-3 copper-clad plate; the reinforcing material is electronic-grade glass fiber cloth or glass felt.
The electronic-grade glass fiber cloth and the glass felt are prepreg raw materials which are conventionally used in the field. According to the common knowledge in the field, when the reinforcing material is electronic-grade glass fiber cloth, the prepreg for the high-toughness halogen-free CEM-3 copper-clad plate is a veneering prepreg; when the reinforcing material is a glass felt, the prepreg for the high-toughness halogen-free CEM-3 copper-clad plate is a sandwich prepreg.
Preferably, in the preparation of the veneered prepreg, the equipment used for coating is a vertical gluing machine, and the coating speed is 16-23 m/min; more preferably 18 to 20 m/min.
Preferably, in the preparation of the sandwich prepreg, equipment for coating the sandwich material is a horizontal gluing machine; the coating speed is 9-13 m/min; more preferably 10 to 12 m/min.
Preferably, the drying temperature is 180-205 ℃; more preferably 190 to 200 ℃.
The invention also provides a prepreg prepared by the preparation method of the prepreg for the high-toughness halogen-free CEM-3 copper-clad plate.
The electronic grade glass fiber cloth can be electronic grade glass fiber cloth conventionally used in the field, and is preferably electronic grade glass fiber cloth 7628. The glass mat may be one conventionally used in the art, preferably 105 g.
The resin content of the veneering prepreg is generally 31-35 wt%. The resin content of the sandwich prepreg is generally 28-33 wt%. The gel time of the veneering prepreg is generally 120-140 s, and the gel time of the glue solution is generally 230-260 s. The fluidity of the veneering prepreg is generally 18-24%. The fluidity of the sandwich prepreg is generally 22-30%. The volatile content of the surfacing prepreg is less than 0.5 percent, such as 0.3 percent, and the volatile content of the sandwich prepreg is less than 0.5 percent, such as 0.3 percent. The gel time of the sandwich prepreg need not be determined as is common in the art.
The invention also provides a preparation method of the high-toughness halogen-free CEM-3 copper-clad plate, which comprises the following steps:
(1) overlapping a plurality of veneering prepregs on two sides of a plurality of sandwich prepregs to obtain a core material, and then covering copper foil on one side or two sides of the core material to obtain a semi-finished board;
(2) and carrying out hot-pressing on the semi-finished plate to obtain the copper-clad plate.
In the invention, the lamination is a conventional method for stacking prepregs in the field of copper-clad plate preparation technology, and a plurality of prepregs with the same size and shape are stacked in order, namely, all sides of the prepregs are stacked in alignment. In the present invention, the stacking does not require pressure, and generally follows four principles: the glue content is high or low, the cloth type is consistent, the structure is symmetrical and the left and right matching principle.
In the step (2), the method and conditions for the hot press pressing may be those conventional in the art. According to the general knowledge in the art, after a steel sheet and a kraft paper are sequentially arranged on a copper foil before hot pressing, hot pressing is performed, and after the hot pressing, the kraft paper and the steel sheet are removed. The number of the kraft paper is generally 18 to 20.
The pressure of the hot pressing is preferably 20 to 34kg/cm2(ii) a More preferably 27 to 32kg/cm2。
The temperature of the hot pressing is preferably 130-200 ℃; more preferably 160 to 190 ℃.
The time for the hot pressing is preferably 130-150 min.
In the invention, the preparation method of the high-toughness halogen-free CEM-3 copper-clad plate generally also carries out subsequent appearance processing and inspection procedures so as to ensure the quality of the product.
The invention also provides a high-toughness halogen-free CEM-3 copper-clad plate prepared by the preparation method of the high-toughness halogen-free CEM-3 copper-clad plate.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
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 glue solution, the prepreg and the preparation method of the high-toughness halogen-free CEM-3 copper-clad plate are all used, and the preparation methods are simple in process, low in cost, stable in technology, low in reject ratio and strong in process controllability and are suitable for mass production.
2. The high-toughness halogen-free CEM-3 copper-clad plate meets the requirement of a downstream PCB (printed Circuit Board) to plate toughness production process, has good comprehensive performance, particularly has good halogen-free, toughness, heat resistance, mechanical strength and thickness uniformity, for example, the bromine content (PPm) is less than 500, and completely reaches the industry ratio standard value of 900; t-288 is more than 60min, which is 50 times higher than that of the common FR-4 halogen-free copper clad laminate. The high-toughness halogen-free CEM-3 copper-clad plate disclosed by the invention is free from layering and foaming in a thermal stress test.
Drawings
Fig. 1 is a photograph of a sample of the drop weight impact test of effect example 1. Wherein, the left side is the copper-clad plate prepared in the embodiment 3; the right side is the same kind of common CEM-3 copper-clad plate.
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.
Example 1
A preparation method of glue solution for a high-toughness halogen-free CEM-3 copper-clad plate comprises the following steps:
the raw material formula is as follows:
resin: 100 parts of novolac epoxy resin, 400 parts of flame-retardant modified liquid halogen-free epoxy resin and 200 parts of flame-retardant modified solid halogen-free epoxy resin; the modified epoxy resin is DOPO type halogen-free flame-retardant epoxy resin, and the product name is as follows: DOPO type, epoxy value: 8.3-9.4(Eq/kg), viscosity 27 ℃ (mPas): 2000-; the flame-retardant modified solid epoxy resin is DOPO type halogen-free flame-retardant epoxy resin, and the product name is as follows: DOPO type, epoxy value: 970-1070(g/eg), viscosity 150 ℃ (mPas): 8000-;
curing agent: 40 parts of Dicyandiamide (DICY);
curing accelerator: 0.20 part of 2-phenylimidazole (substituted by C-2);
solvent: 150 parts of an organic solvent (acetone: butanone: DMF: propylene glycol methyl ether ═ 1: 1: 6: 1).
The preparation method comprises the following steps: mixing a curing agent, an accelerator and a solvent, and stirring at the rotating speed of 1000rpm for 4 hours until the curing agent, the accelerator and the solvent are completely dissolved to obtain a mixture A; (2) mixing the mixture A with the flame-retardant modified liquid halogen-free epoxy resin and the flame-retardant modified solid halogen-free epoxy resin, and stirring at the rotating speed of 1300rpm for 5 hours until the mixture is uniformly stirred to obtain a mixture B; (3) and (3) mixing the mixture B with the novolac epoxy resin under the stirring condition, stirring at the high speed of 2300rpm for 2 hours, stirring at the rotating speed of 1000rpm for 10 hours, and curing to obtain the gel solution, wherein the gel time of the gel solution is 230 s.
High-toughness halogen-free CEM-3 copper-clad plate
The preparation method comprises the following steps: gluing: coating the prepared high-toughness halogen-free glue solution for the CEM-3 copper-clad plate on 2 pieces of electronic grade glass fiber cloth 7628 (serving as a plate facing material) and 1 piece of 105g of glass felt (serving as a sandwich) by using a gluing machine; the oven temperature of the gluing machine is 190 ℃, the speed of gluing the facing material is 20m/min, 2 prepregs are obtained, the resin content of the prepregs is 32 wt%, the gelling time of the prepregs is 130s, the fluidity of the prepregs is 22%, and the volatile matter of the prepregs is 0.3%. The speed of gluing the sandwich material is 11m/min, 1 prepreg is obtained, the resin content of the prepreg is 29 wt%, the fluidity of the prepreg is 26%, and the volatile matter of the prepreg is 0.3%;
and (2) laminating: overlapping 3 prepregs, and covering copper foils on two surfaces to obtain a semi-finished product;
thirdly, hot-pressing the semi-finished product at 190 ℃ under the pressure of 30kg/cm2And hot pressing for 143 min.
The obtained copper-clad plate was subjected to performance measurement, and the results are shown in table 1.
Table 1 performance parameters of copper clad laminate in example 1
As can be seen from Table 1, the copper-clad plate prepared in example 1 has good comprehensive properties.
Example 2
A preparation method of glue solution for a high-toughness halogen-free CEM-3 copper-clad plate comprises the following steps:
the raw material formula is as follows:
resin: 80 parts of phenolic epoxy resin, 300 parts of flame-retardant modified liquid halogen-free epoxy resin and 150 parts of flame-retardant modified solid halogen-free epoxy resin; the flame-retardant modified epoxy resin is DOPO type halogen-free flame-retardant epoxy resin, and the product name is as follows: DOPO type, epoxy value: 8.3-9.4(Eq/kg), viscosity 27 ℃ (mPas): 2000-; the flame-retardant modified solid epoxy resin is DOPO type halogen-free flame-retardant epoxy resin, and the product name is as follows: DOPO type, epoxy value: 970-1070(g/eg), viscosity 150 ℃ (mPas): 8000-;
curing agent: 30 parts of Dicyandiamide (DICY);
curing accelerator: 0.20 part of 2-phenylimidazole (substituted by C-2);
solvent: 120 parts of an organic solvent (acetone: butanone: dimethylformamide: propylene glycol methyl ether ═ 1: 1: 6: 1).
The preparation method comprises the following steps: mixing a curing agent, an accelerator and a solvent, and stirring at the rotating speed of 1000rpm for 4 hours until the curing agent, the accelerator and the solvent are completely dissolved to obtain a mixture A; (2) mixing the mixture A with the flame-retardant modified liquid halogen-free epoxy resin and the flame-retardant modified solid halogen-free epoxy resin, and stirring at the rotating speed of 1300rpm for 5 hours until the mixture is uniformly stirred to obtain a mixture B; (3) and under the stirring condition, mixing the mixture B with the novolac epoxy resin, stirring at the rotating speed of 2500rpm for 2 hours at a high speed, stirring at the rotating speed of 1000rpm for 9 hours, and curing to obtain the gel solution, wherein the gel time of the gel solution is 245 s.
High-toughness halogen-free CEM-3 copper-clad plate
The preparation method comprises the following steps: gluing: coating the prepared high-toughness halogen-free glue solution for the CEM-3 copper-clad plate on 2 pieces of electronic grade glass fiber cloth 7628 (serving as a plate facing material) and 1 piece of 105g of glass felt (serving as a sandwich) by using a gluing machine; the oven temperature of the gluing machine is 195 ℃, the speed of gluing the facing material is 20m/min, and 2 prepregs are obtained; the resin content of the prepreg was 32 wt%, the gel time of the prepreg was 133s, the fluidity of the prepreg was 21%, and the volatile matter of the prepreg was 0.3%. The speed of gluing the core material is 12m/min, 1 prepreg is obtained, the resin content of the prepreg is 30 wt%, the fluidity of the prepreg is 27%, and the volatile matter of the prepreg is 0.3%.
And (2) laminating: overlapping 6 prepregs, and covering copper foils on two surfaces to obtain a semi-finished product;
thirdly, hot-pressing the semi-finished product at 195 ℃ under the pressure of 30kg/cm2And carrying out hot pressing for 145min to obtain the product. The obtained copper-clad plate was subjected to performance measurement, and the results are shown in table 2.
Table 2 copper clad laminate performance parameters of example 2
As can be seen from Table 2, the copper-clad plate prepared in example 2 has good comprehensive properties.
Example 3
A preparation method of glue solution for a high-toughness halogen-free CEM-3 copper-clad plate comprises the following steps:
the raw material formula is as follows:
resin: 120 parts of novolac epoxy resin, 450 parts of flame-retardant modified liquid halogen-free epoxy resin and 250 parts of flame-retardant modified solid halogen-free epoxy resin; the flame-retardant modified epoxy resin is DOPO type halogen-free flame-retardant epoxy resin, and the product name is as follows: DOPO type, epoxy value: 8.3-9.4(Eq/kg), viscosity 27 ℃ (mPas): 2000-; the flame-retardant modified solid epoxy resin is DOPO type halogen-free flame-retardant epoxy resin, and the product name is as follows: DOPO type, epoxy value: 970-1070(g/eg), viscosity 150 ℃ (mPas): 8000-;
curing agent: 50 parts of Dicyandiamide (DICY);
curing accelerator: 0.30 part of 2-phenylimidazole (C-2 substituted);
solvent: 200 parts of an organic solvent (acetone: butanone: dimethylformamide: propylene glycol methyl ether ═ 1: 1: 6: 1).
The preparation method comprises the following steps: mixing a curing agent, an accelerator and a solvent, and stirring at the rotating speed of 1000rpm for 4 hours until the curing agent, the accelerator and the solvent are completely dissolved to obtain a mixture A; (2) mixing the mixture A with the flame-retardant modified liquid halogen-free epoxy resin and the flame-retardant modified solid halogen-free epoxy resin, and stirring at the rotating speed of 1300rpm for 4 hours until the mixture is uniformly stirred to obtain a mixture B; (3) and mixing the mixture B with the novolac epoxy resin under the stirring condition, stirring at the rotating speed of 2400rpm for 2 hours at a high speed, stirring at the rotating speed of 1600rpm for 12 hours, and curing to obtain the gel solution, wherein the gel time of the gel solution is 260 s.
Secondly, a preparation method of the high-toughness halogen-free CEM-3 copper-clad plate comprises the following steps: gluing: coating the prepared high-toughness halogen-free glue solution for the CEM-3 copper-clad plate on 2 pieces of electronic grade glass fiber cloth 7628 (serving as a plate facing material) and 1 piece of 105g of glass felt (serving as a sandwich) by using a gluing machine; the oven temperature of the gluing machine is 200 ℃, the speed of gluing the facing material is 21m/min, and 2 prepregs are obtained; the resin content of the prepreg was 33 wt%, the gel time of the prepreg was 135s, the fluidity of the prepreg was 20%, and the volatile matter of the prepreg was 0.3%. The speed of gluing the sandwich material is 11m/min, 1 prepreg is obtained, the resin content of the prepreg is 31 wt%, the fluidity of the prepreg is 29%, and the volatile matter of the prepreg is 0.3%.
And (2) laminating: overlapping 6 prepregs, and covering copper foils on two surfaces to obtain a semi-finished product;
thirdly, carrying out hot-pressing on the semi-finished product, wherein the temperature of the hot-pressing is 185 ℃, and the pressure of the hot-pressing is 31kg/cm2And hot pressing for 148 min.
Effect example 1
The high-toughness halogen-free CEM-3 copper-clad plate of example 3 was subjected to performance testing, and the main performance results are shown in Table 3 below. Other embodiments have similar effects. The detection methods are all conventional detection methods.
Table 3 performance parameters of copper clad laminate of example 3
Drop hammer impact test (toughness test)
An experimental instrument: ISO Impact Tester, model BYK Gardner, model 5512;
experimental samples: the thickness of the base material is 1.0 mm-1.1 mm, and the base material structure is 7628 multiplied by 1+105g felt multiplied by 1+7628 multiplied by 1 ply;
the experimental process comprises the following steps: and (3) installing the etched sample according to the requirement of an instrument, fixing the drop hammer at the position with the height of 20mm, enabling the drop hammer to freely fall to impact the material, and indicating that the toughness and the Punch effect of the material are better if the cross crack generated by the impact of the drop hammer on the material is clearer. Fig. 1 is a photograph of a sample of the drop weight impact test. As can be seen from FIG. 1, the toughness of the copper clad laminate (on the left side of FIG. 1) prepared in the embodiment 3 of the invention is obviously superior to that of the similar common CEM-3 copper clad laminate (on the right side of FIG. 1) in the market.
Claims (11)
1. A high-toughness halogen-free CEM-3 copper-clad plate is characterized by being prepared by the following method:
(1) overlapping and matching a plurality of sticking surface prepregs on two sides of a plurality of sandwich prepregs to obtain a core material, and then covering copper foil on one side or two sides of the core material to obtain a semi-finished plate;
(2) carrying out hot pressing on the semi-finished plate to obtain the composite material;
the sandwich prepreg is prepared by the following method: coating glue solution for a high-toughness halogen-free CEM-3 copper-clad plate on a glass felt, and then drying to obtain the high-toughness halogen-free CEM-3 copper-clad plate;
the veneered prepreg is prepared by the following method: coating glue solution for a high-toughness halogen-free CEM-3 copper-clad plate on electronic-grade glass fiber cloth, and then drying to obtain the high-toughness halogen-free CEM-3 copper-clad plate;
the glue solution for the high-toughness halogen-free CEM-3 copper-clad plate is prepared from the following raw materials in parts by weight: 75-120 parts of phenolic epoxy resin, 300-450 parts of flame-retardant modified liquid halogen-free epoxy resin, 150-250 parts of flame-retardant modified solid halogen-free epoxy resin, 25-50 parts of curing agent, 0.10-0.30 part of curing accelerator and 100-200 parts of organic solvent;
the flame-retardant modified liquid halogen-free epoxy resin is DOPO type liquid halogen-free flame-retardant epoxy resin;
the flame-retardant modified solid halogen-free epoxy resin is DOPO type solid halogen-free flame-retardant epoxy resin;
the performance indexes of the DOPO type liquid halogen-free flame-retardant epoxy resin are as follows: the epoxy equivalent is 320-360g/eq, the viscosity at 25 ℃ is 1800-3000 mPa-s, and the phosphorus content is 3.1%;
the DOPO type solid halogen-free flame-retardant epoxy resin has the following performance indexes: an epoxy equivalent of 970-1070g/eq and a viscosity at 150 ℃ of 8000-11000 mPas.
2. The high-toughness halogen-free CEM-3 copper-clad plate of claim 1, wherein the curing agent is dicyandiamide;
and/or the curing accelerator is diphenyl imidazole;
and/or the organic solvent is one or more of acetone, butanone, dimethylformamide and propylene glycol methyl ether.
3. The high-toughness halogen-free CEM-3 copper-clad plate of claim 2, wherein the weight ratio of acetone, butanone, dimethylformamide and propylene glycol methyl ether is 1: 1: 6: 1.
4. the high-toughness halogen-free CEM-3 copper-clad plate according to any one of claims 1 to 3, wherein the glue solution for the high-toughness halogen-free CEM-3 copper-clad plate is prepared by the following method:
(1) mixing the curing agent, the curing accelerator and the organic solvent, and stirring until the curing agent, the curing accelerator and the organic solvent are dissolved to obtain a mixture A;
(2) mixing the mixture A, the flame-retardant modified liquid halogen-free epoxy resin and the flame-retardant modified solid halogen-free epoxy resin, and uniformly stirring to obtain a mixture B;
(3) and mixing the mixture B with the novolac epoxy resin under the stirring condition, shearing at the speed of 2200-2800 rpm, and curing to obtain the high-toughness halogen-free CEM-3 copper-clad plate glue solution.
5. The high-toughness halogen-free CEM-3 copper-clad plate according to claim 4, wherein in the step (1), the stirring time is 3 to 5 hours;
and/or in the step (1), the rotating speed of stirring is 900-1400 rpm;
and/or in the step (2), the stirring time is 3-5 hours;
and/or in the step (2), the rotating speed of the stirring is 1000-1500 rpm;
and/or in the step (3), the shearing time is 1.0-2.0 hours;
and/or in the step (3), the shearing rotating speed is 2300-2700 rpm;
and/or in the step (3), the curing is carried out by stirring for 8-12 hours at the rotating speed of 1000-1600 rpm.
6. The high-toughness halogen-free CEM-3 copper-clad plate of claim 1, wherein said electronic-grade glass fiber cloth is electronic-grade glass fiber cloth 7628;
and/or, the glass mat is 105g glass mat;
and/or, in the preparation of the veneered prepreg, the equipment used for coating is a vertical gluing machine;
and/or in the preparation of the sandwich prepreg, the equipment used for coating is a horizontal gluing machine.
7. The high-toughness halogen-free CEM-3 copper-clad plate according to claim 6, wherein in the preparation of the veneering prepreg, the coating speed is 16-23 m/min;
and/or in the preparation of the sandwich prepreg, the coating speed is 9-13 m/min.
8. The high-toughness halogen-free CEM-3 copper-clad plate according to claim 6, wherein in the preparation of the veneering prepreg, the coating speed is 18-20 m/min;
and/or in the preparation of the sandwich prepreg, the coating speed is 10-12 m/min.
9. The high-toughness halogen-free CEM-3 copper-clad plate according to any one of claims 6 or 7, wherein the resin content of the veneering prepreg is 31-35 wt%; the gel time of the veneering prepreg is 120-140 s; the fluidity of the veneering prepreg is 18-24%; the volatile content of the veneering prepreg is less than 0.5;
and/or the resin content of the sandwich prepreg is 28-33 wt%; the fluidity of the sandwich prepreg is 22-30%; the volatile component of the sandwich prepreg is less than 0.5.
10. The high-toughness halogen-free CEM-3 copper-clad plate according to claim 1, wherein the pressure of the hot-pressing in the step (2) is 20-34 kg/cm2；
And/or the temperature of the hot pressing is 130-200 ℃;
and/or the time for hot pressing is 130-150 min.
11. The high-toughness halogen-free CEM-3 copper-clad plate according to claim 1, wherein the pressure of the hot-pressing in the step (2) is 27 to 32kg/cm2；
And/or the temperature of the hot pressing is 160-190 ℃.
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| CN107771418B true CN107771418B (en) | 2021-12-17 |
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| CN111703171A (en) * | 2020-05-09 | 2020-09-25 | 江苏诺德新材料股份有限公司 | Processing production process of 5G high-frequency microwave copper-clad plate |
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| CN202878829U (en) * | 2012-09-21 | 2013-04-17 | 浙江恒誉电子科技有限公司 | High-CTI (Comparative Tracking Index) CEM-3 (Composite Epoxy Material Grade-3) copper-clad plate |
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| US9005761B2 (en) * | 2011-12-22 | 2015-04-14 | Elite Material Co., Ltd. | Halogen-free resin composition and its application for copper clad laminate and printed circuit board |
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| CN1488672A (en) * | 2003-08-01 | 2004-04-14 | 广州宏昌电子材料工业有限公司 | Halogen-free flame-retarding epoxy resin composition containing phosphor and nitrogen and preimpregnated material and laminate containing same |
| CN101343401A (en) * | 2008-08-22 | 2009-01-14 | 腾辉电子（苏州）有限公司 | Halogen-free glue solution, halogen-free flame-proof cover copper foil substrate using the glue solution and preparation method thereof |
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| CN202878829U (en) * | 2012-09-21 | 2013-04-17 | 浙江恒誉电子科技有限公司 | High-CTI (Comparative Tracking Index) CEM-3 (Composite Epoxy Material Grade-3) copper-clad plate |
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