CN116874982A - high-Tg copper-clad plate and preparation method thereof - Google Patents
high-Tg copper-clad plate and preparation method thereof Download PDFInfo
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- CN116874982A CN116874982A CN202310789329.XA CN202310789329A CN116874982A CN 116874982 A CN116874982 A CN 116874982A CN 202310789329 A CN202310789329 A CN 202310789329A CN 116874982 A CN116874982 A CN 116874982A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000003822 epoxy resin Substances 0.000 claims abstract description 31
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 31
- 239000011256 inorganic filler Substances 0.000 claims abstract description 29
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 29
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 40
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 36
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 36
- 239000004744 fabric Substances 0.000 claims description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 229910052802 copper Inorganic materials 0.000 claims description 29
- 239000010949 copper Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 29
- 239000011521 glass Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 23
- 239000003292 glue Substances 0.000 claims description 22
- 238000005470 impregnation Methods 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 20
- 238000010030 laminating Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 239000011889 copper foil Substances 0.000 claims description 11
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 10
- 239000002655 kraft paper Substances 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 6
- 230000009257 reactivity Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 50
- 230000000052 comparative effect Effects 0.000 description 26
- 238000010998 test method Methods 0.000 description 18
- 239000005340 laminated glass Substances 0.000 description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009662 stress testing Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 238000007232 Eastwood olefination reaction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 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 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 phenolic aldehyde Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
Classifications
-
- 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
- C08K3/38—Boron-containing compounds
-
- 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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- 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
-
- 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
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
-
- 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
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- 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)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
Abstract
The application discloses a high Tg copper-clad plate, which comprises the following components in parts by weight: 350 to 450 parts of brominated epoxy resin, 7 to 10 parts of dicyandiamide, 0.1 to 0.25 part of curing accelerator, 70 to 90 parts of solvent, 35 to 60 parts of inorganic filler and 0.5 to 1 part of silane coupling agent. The application also discloses a preparation method of the high Tg copper-clad plate. According to the high Tg copper-clad plate provided by the application, through the synergistic effect of inorganic filler with specific type and specific proportion and brominated epoxy resin, solvent and the like, the copper-clad plate has the advantages of higher glass transition temperature, high CTI value, good reactivity and the like; the method is used for preparing the printed circuit board, so that the copper-clad plate has good reliability, mechanical processing performance and extremely high tracking index, and can well meet the processing performance of the PCB on products.
Description
Technical Field
The application belongs to the technical field of copper-clad plate preparation, and particularly relates to a high Tg copper-clad plate and a preparation method thereof.
Background
The copper foil substrate (Copper Clad Laminate, CCL) is the main material for manufacturing Printed Circuit Boards (PCBs) and is thus also an essential basic electronic material for any electronic products. With the rapid development of the PCB industry, the market demand of the high-performance copper-clad laminate is increased, the high-performance copper-clad laminate is comprehensively developed in the lead-free age until now, besides the performances such as heat resistance, glass transition temperature (Tg) value, coefficient of thermal expansion (CTE value) and the like of the product are concerned, the toughness, PCB processing property and cohesiveness of the material become important points of great concern, and the balance of the performances of the copper-clad laminate substrate is developed into an important development trend of developing novel copper-clad laminate materials.
Nowadays, the demands of light, thin, short, small and digital electronic products are mainly developed in the direction of miniaturization, multifunction, high performance and high reliability, so that the PCB design is toward high multilayering, fine patterning and high density, and the demands of the processes such as line width, line spacing, aperture, hole wall and the like in the PCB industry are also gradually developed toward high integration, high density and high multilayering. For example, the mainstream high density interconnect laminate (HDI) requires a micro-via hole diameter of 6mil or less, a micro-via ring diameter of 0.35mm or less,the contact density is 130in/m 2 The wiring density was 117in/m 2 The line width/line distance is below 0.1mm/0.1mm, and the high-order HDI (more than twelve layers) is required to bear special processes such as high-order multiple hot pressing and the like and more accurate and fine process requirements. With the development of high-density mounting technology, especially the full-scale promotion of leadless and the rapid development of Surface Mount Technology (SMT), in PCB processing and complete machine accessory mounting, the times and temperature of repeated thermal shock bearing of materials are higher than the traditional requirements, and all the problems are finally converted into great challenges of the reliability of the high-performance copper clad laminate.
The Tg of the material means that the high polymer is converted into a soft rubbery state from a hard glass state at normal temperature in the heating process, the material is in a hard solid state below the Tg temperature, and has some mechanical strength, when the material is above the Tg temperature, a molecular chain segment starts to move, the material is softened, the high-elastic state is characterized, meanwhile, specific volume, specific heat, insulativity and dielectric loss are greatly changed, the electrical property is greatly reduced, and if the Tg of the material is too low, the use temperature and application range of the material are greatly limited, and the material cannot meet the requirements of high-end markets.
Disclosure of Invention
The present application aims to solve at least one of the technical problems in the related art to some extent. Therefore, the application mainly aims to provide a high Tg copper-clad plate and a preparation method thereof, and aims to solve the technical problem that the existing copper-clad plate cannot adapt to the requirements of high-end markets due to poor comprehensive performance.
The application aims at realizing the following technical scheme:
the high Tg copper-clad plate comprises the following components in parts by weight: 350 to 450 parts of brominated epoxy resin, 7 to 10 parts of dicyandiamide, 0.1 to 0.25 part of curing accelerator, 70 to 90 parts of solvent, 35 to 60 parts of inorganic filler and 0.5 to 1 part of silane coupling agent.
Preferably, the composition comprises the following components in parts by weight: 380-420 parts of brominated epoxy resin, 7-9 parts of dicyandiamide, 0.1-0.2 part of curing accelerator, 75-85 parts of solvent, 48-55 parts of inorganic filler and 0.6-0.8 part of silane coupling agent.
More preferably, the composition comprises the following components in parts by weight: 400 parts of brominated epoxy resin, 8.6 parts of dicyandiamide, 0.17 part of a curing accelerator, 80 parts of a solvent, 40 parts of an inorganic filler and 0.7 part of a silane coupling agent.
Preferably, wherein the curing accelerator is one or more of 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole.
Preferably, the solvent is one or more of dimethylformamide, acetone and methyl ethyl ketone.
Preferably, the inorganic filler is a mixture of zinc borate and aluminum hydroxide according to the weight ratio of 1-3:3-8.
More preferably, wherein the inorganic filler is zinc borate and aluminum hydroxide according to parts by weight (2-3): 8, forming a mixture.
More preferably, the inorganic filler is a mixture of zinc borate and aluminum hydroxide according to a weight ratio of 3:8.
Preferably, the particle sizes of the zinc borate and the aluminum hydroxide are 3-15 μm.
In a second aspect, the application also provides a preparation method of the high Tg copper-clad plate, which comprises the following steps:
and (3) glue preparation: according to the formula requirement, mixing the solvent with the brominated epoxy resin, stirring, continuously adding dicyandiamide, a curing accelerator, an inorganic filler and a silane coupling agent after stirring uniformly, and stirring until the materials are completely dissolved to form a prepreg;
impregnation: pouring the presoaked material with the glue into an impregnation tank, impregnating the presoaked material with glass cloth, and baking the presoaked material for 3 to 10 minutes at the temperature of 160 to 220 ℃; and (3) superposing one or more layers of the baked glass cloth, coating copper foil on two sides of the superposed glass cloth, and laminating with 8-12 kraft paper at the temperature of 130-195 ℃ under the pressure of 0.4-3.7 MPa for 120-160 min to obtain the high Tg copper-clad plate.
Compared with the prior art, the application has at least the following advantages:
1) The copper-clad plate has the advantages of higher glass transition temperature, high CTI value, good reactivity and the like by adopting inorganic filler with specific type and specific proportion to cooperate with brominated epoxy resin, solvent and the like; the method is used for preparing the printed circuit board, so that the copper-clad plate has good reliability, mechanical processing performance and extremely high tracking index.
2) The high Tg copper-clad plate prepared by the preparation method can effectively raise the glass transition temperature of the copper-clad plate by more than 10 ℃, can effectively raise CTI index to more than 500V-600V, and can well meet the processing performance of the PCB on products.
3) The preparation method of the high Tg copper-clad plate can be effectively applied to different curing agent systems, including but not limited to Dicy (dicyandiamide), phenolic aldehyde, amine and the like.
Detailed Description
The application will now be further described in detail with reference to the following examples, which are intended to be illustrative only and not limiting in any way.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as an upper range limit, or as a lower range limit, it is to be understood that any range is specifically disclosed by combining any pair of the upper range limit or preferred value with any lower range limit or preferred value, regardless of whether the range is specifically disclosed. Unless otherwise indicated, the numerical range values set forth herein are intended to include the endpoints of the range, and all integers and fractions within the range.
All percentages, parts, ratios, etc. herein are by weight unless otherwise specified.
The materials, methods, and examples herein are illustrative and, unless otherwise indicated, should not be construed as limiting.
The application provides a technical scheme that: the high Tg copper-clad plate comprises, by weight, 350-450 parts of brominated epoxy resin, 7-10 parts of dicyandiamide, 0.1-0.25 part of a curing accelerator, 70-90 parts of a solvent, 35-60 parts of an inorganic filler and 0.5-1 part of a silane coupling agent.
In the following examples, the brominated epoxy resin is selected from high-bromine or low-bromine epoxy resin, the brominated epoxy resin adopted in the examples of the application is selected from low-bromine epoxy resin, specifically, nanya epoxy resin NPEB454A80, the epoxy equivalent is 425-445, and the bromine content is 19%; the silane coupling agent in the following examples is specifically KH-560, which is mainly used as a coupling agent.
Wherein the curing accelerator is one or more of 2-methylimidazole, 2-phenylimidazole and 2-ethyl-4-methylimidazole.
Wherein the solvent is one or more of dimethylformamide, acetone and methyl ethyl ketone.
Wherein the inorganic filler is a mixture of zinc borate and aluminum hydroxide according to the weight ratio of 1-3:3-8, and is further preferable: the weight part ratio of zinc borate to aluminum hydroxide is (2-3): 8, more preferably 3:8;
wherein the particle diameters of the zinc borate and the aluminum hydroxide are each 3 to 15 μm, more preferably 2 to 6 μm,
the particle size of the inorganic filler is too large, such as more than 10um, which easily causes aggregation and sedimentation of particles in the glue; too small particle size of <3um is likely to cause rapid viscosity rise of the glue to affect impregnation smoothness.
The application also provides a preparation method of the high Tg copper-clad plate, which specifically comprises the following steps:
and (3) glue preparation: stirring 70-90 parts of solvent and 350-450 parts of brominated epoxy resin in a beaker according to parts by weight, continuously adding 7-10 parts of dicyandiamide, 0.1-0.25 part of curing accelerator, 35-60 parts of inorganic filler and 0.5-1 part of silane coupling agent after stirring uniformly, and stirring until the components are completely dissolved to form prepreg;
impregnation: pouring the presoaked material with the glue into an impregnation tank, impregnating the presoaked material with glass cloth, and baking the presoaked material for 3 to 10 minutes at the temperature of 160 to 220 ℃; and (3) superposing one or more layers of the baked glass cloth, coating copper foil on two sides of the superposed glass cloth, and laminating with 8-12 kraft paper at the temperature of 130-195 ℃ under the pressure of 0.4-3.7 MPa for 120-160 min to obtain a sample of the high Tg copper-clad plate.
And (3) testing: and taking out the high Tg copper clad laminate, testing according to each testing method, and recording testing data.
The test method adopted by the application comprises the following steps:
the influence of the inorganic filler on the DICY/brominated epoxy resin system is reflected by testing the main properties of each test sample respectively. The main properties tested in this experiment are glass transition temperature, peel strength, heat resistance, CTI test, etc.
1. Glass transition temperature test:
the samples were tested for glass transition temperature as described in IPC-TM-650.2.4.24 using the differential scanning test method.
2. Peel strength test:
the substrate samples were processed to a 50.8x50.8mm pattern and the samples were tested for receptive status as described in IPC-TM-650.2.4.8.
3. Thermal stress testing
The substrate samples were processed to a 50.8x50.8mm pattern and the samples were subjected to thermal stress testing as described in IPC-TM-650 2.4.13.1.
4. Thermal delamination time (T260) test
The samples were tested for thermal stratification time as described in IPC-TM-650.2.4.24.1, measured by TMA.
5. Thermal decomposition temperature (Td) test
The samples were tested for thermal decomposition temperature as described in IPC-TM-650.2.4.24, measured by thermogravimetric analysis.
6. Comparative Tracking Index (CTI) test
The samples were subjected to comparative tracking index testing according to IEC60112 method.
7. Electrical performance testing
Dielectric constant
The dielectric constant and dielectric loss tangent were measured by a two-fluid slot method, and specific test methods are: IPC-TM-650 2.5.5.3; the sample preparation steps at the time of the test are:
preparing 3 etched and cleaned samples, wherein the size of the samples is 80 mm or 30mm, and the thickness is less than 0.8;
treating for more than 24 hours at the temperature of 23 ℃ and the relative humidity of 50 ℃ and 5 percent before testing;
opening electrodes in the test groove, and blowing dust or silicone oil by clean compressed air;
1. inputting the width and thickness of a standard sample, and testing whether the standard sample value is in a range;
2. measuring the width and thickness of the sample by using a micrometer, and inputting the width and thickness into software; when the cavity is not filled with the sample, the stress is firstly removed, and then the sample is filled into the cavity to start testing;
3. the average of 3 samples was calculated after the test results were taken.
Example 1
The high Tg copper-clad plate provided by the embodiment is obtained by the following preparation method:
and (3) glue preparation: 70 parts of dimethylformamide and 350 parts of brominated epoxy resin are stirred in a beaker according to parts by weight, 7 parts of dicyandiamide, 0.1 part of 2-methylimidazole, 28 parts of aluminum hydroxide, 7 parts of zinc borate and 0.5 part of silane coupling agent are continuously added after the stirring is carried out uniformly, and the mixture is stirred until the mixture is completely dissolved to form prepreg, wherein in the embodiment, the particle size of zinc borate is 5um, and the particle size of aluminum hydroxide is 3um.
Impregnation: pouring the presoaked liquid with the glue into an impregnation tank, impregnating the presoaked liquid with glass cloth, and baking the presoaked liquid for 9min at 160 ℃; and (3) laminating one layer of baked glass cloth, covering copper foils on two sides of the laminated glass cloth, and laminating with 9 kraft paper at the temperature of 150 ℃ under the pressure of 0.7MPa for 150min to obtain a sample of the high Tg copper-clad plate.
And (3) testing: the high Tg copper clad laminate was taken out and tested according to each test method, and the test data were recorded as shown in Table 1.
Example 2
The high Tg copper-clad plate provided by the embodiment is obtained by the following preparation method:
and (3) glue preparation: 80 parts of dimethylformamide and 400 parts of brominated epoxy resin are stirred in a beaker according to parts by weight, 8.6 parts of dicyandiamide, 0.17 part of 2-methylimidazole, 35 parts of aluminum hydroxide, 5 parts of zinc borate and 0.7 part of silane coupling agent are continuously added after the stirring is uniform, and the mixture is stirred until the mixture is completely dissolved to form a prepreg, wherein in the embodiment, the particle size of zinc borate is 10um, and the particle size of aluminum hydroxide is 14um.
Impregnation: pouring the presoaked liquid with the glue into an impregnation tank, impregnating the presoaked liquid with glass cloth, and baking the presoaked liquid for 8 minutes at the temperature of 190 ℃; and (3) laminating the baked glass cloth layers together, covering copper foils on two sides of the laminated glass cloth, laminating the laminated glass cloth layers with 10 kraft paper sheets at the temperature of 140 ℃ under the pressure of 3.5MPa for 140min, and thus obtaining a sample of the high Tg copper-clad plate.
And (3) testing: the high Tg copper clad laminate was taken out and tested according to each test method, and the test data were recorded as shown in Table 1.
Example 3
The high Tg copper-clad plate provided by the embodiment is obtained by the following preparation method:
and (3) glue preparation: 80 parts of dimethylformamide and 400 parts of brominated epoxy resin are stirred in a beaker according to parts by weight, 8.6 parts of dicyandiamide, 0.17 part of 2-methylimidazole, 30 parts of aluminum hydroxide, 10 parts of zinc borate and 0.7 part of silane coupling agent are continuously added after the stirring is uniform, and the mixture is stirred until the mixture is completely dissolved to form a prepreg, wherein in the embodiment, the particle size of zinc borate is 8um, and the particle size of aluminum hydroxide is 10um.
Pouring the presoaked liquid with the glue into an impregnation tank, impregnating the presoaked liquid with glass cloth, and baking for 4min at 190 ℃; and (3) laminating the baked glass cloth layers together, covering copper foils on two sides of the laminated glass cloth, laminating the laminated glass cloth layers with 10 kraft paper sheets at the temperature of 140 ℃ under the pressure of 2.8MPa for 160min, and thus obtaining a sample of the high Tg copper-clad plate.
And (3) testing: the high Tg copper clad laminate was taken out and tested according to each test method, and the test data were recorded as shown in Table 1.
Example 4
The high Tg copper-clad plate provided by the embodiment is obtained by the following preparation method:
and (3) glue preparation: 80 parts of dimethylformamide and 400 parts of brominated epoxy resin are stirred in a beaker according to parts by weight, 8.6 parts of dicyandiamide, 0.17 part of 2-methylimidazole, 25 parts of aluminum hydroxide, 15 parts of zinc borate and 0.7 part of silane coupling agent are continuously added after the stirring is uniform, and the mixture is stirred until the mixture is completely dissolved to form a prepreg, wherein in the embodiment, the particle size of zinc borate is 10um, and the particle size of aluminum hydroxide is 12um.
Impregnation: pouring the presoaked liquid with the glue into an impregnation tank, impregnating the presoaked liquid with glass cloth, and baking the presoaked liquid for 6 minutes at the temperature of 200 ℃; and (3) laminating the baked glass cloth layers together, covering copper foils on two sides of the laminated glass cloth, laminating with 11 kraft paper sheets at 160 ℃ under 1.2MPa for 150min, and obtaining a sample of the high Tg copper-clad plate.
And (3) testing: the high Tg copper clad laminate was taken out and tested according to each test method, and the test data were recorded as shown in Table 1.
Example 5
The high Tg copper-clad plate provided by the embodiment is obtained by the following preparation method:
and (3) glue preparation: 80 parts of dimethylformamide and 400 parts of brominated epoxy resin are stirred in a beaker according to parts by weight, 8.6 parts of dicyandiamide, 0.17 part of 2-methylimidazole, 40 parts of aluminum hydroxide, 10 parts of zinc borate and 0.7 part of silane coupling agent are continuously added after the stirring is uniform, and the mixture is stirred until the mixture is completely dissolved to form a prepreg, wherein in the embodiment, the particle size of zinc borate is 5um, and the particle size of aluminum hydroxide is 8um.
Impregnation: pouring the presoaked liquid with the glue into an impregnation tank, impregnating the presoaked liquid with glass cloth, and baking the presoaked liquid for 9 minutes at the temperature of 210 ℃; and (3) laminating the baked glass cloth layers together, covering copper foils on two sides of the laminated glass cloth, laminating the laminated glass cloth layers with 12 kraft paper at the temperature of 185 ℃ under the pressure of 2.0MPa for 150min, and obtaining a sample of the high Tg copper-clad plate.
And (3) testing: the high Tg copper clad laminate was taken out and tested according to each test method, and the test data were recorded as shown in Table 1.
Example 6
The high Tg copper-clad plate provided by the embodiment is obtained by the following preparation method:
and (3) glue preparation: 80 parts of dimethylformamide and 400 parts of brominated epoxy resin are stirred in a beaker according to parts by weight, 8.6 parts of dicyandiamide, 0.17 part of 2-methylimidazole, 40 parts of aluminum hydroxide, 15 parts of zinc borate and 0.7 part of silane coupling agent are continuously added after the stirring is uniform, and the mixture is stirred until the mixture is completely dissolved to form a prepreg, wherein in the embodiment, the particle size of zinc borate is 6um, and the particle size of aluminum hydroxide is 6um.
Impregnation: pouring the presoaked liquid with the glue into an impregnation tank, impregnating the presoaked liquid with glass cloth, and baking the presoaked liquid for 6 minutes at the temperature of 210 ℃; and (3) laminating the baked glass cloth layers together, and finally covering copper foils on two sides of the laminated glass cloth, and laminating with 10 kraft paper at 2.5MPa and 160 ℃ for 150min to obtain a sample of the high Tg copper-clad plate.
And (3) testing: the high Tg copper clad laminate was taken out and tested according to each test method, and the test data were recorded as shown in Table 1.
Example 7
The high Tg copper-clad plate provided by the embodiment is obtained by the following preparation method:
and (3) glue preparation: 90 parts of dimethylformamide and 450 parts of brominated epoxy resin are stirred in a beaker according to parts by weight, 9 parts of dicyandiamide, 0.2 part of 2-methylimidazole, 40 parts of aluminum hydroxide, 15 parts of zinc borate and 0.8 part of silane coupling agent are continuously added after the stirring is uniform, and the mixture is stirred until the mixture is completely dissolved to form prepreg, wherein the particle size of zinc borate is 13um, and the particle size of aluminum hydroxide is 15um.
Impregnation: pouring the presoaked liquid with the glue into an impregnation tank, impregnating the presoaked liquid with glass cloth, and baking the presoaked liquid for 6 minutes at the temperature of 210 ℃; and (3) laminating the baked glass cloth layers together, and finally covering copper foils on two sides of the laminated glass cloth, and laminating with 10 kraft paper at 2.5MPa and 160 ℃ for 150min to obtain a sample of the high Tg copper-clad plate.
And (3) testing: the high Tg copper clad laminate was taken out and tested according to each test method, and the test data were recorded as shown in Table 1.
Comparative example 1
The high Tg copper-clad plate provided in this comparative example has the same composition and proportion as in example 2, except that it does not contain aluminum hydroxide and zinc borate; the preparation method is the same as that of the example 2;
and (3) testing: the high Tg copper clad laminate was taken out and tested according to each test method, and the test data were recorded as shown in Table 1.
Comparative example 2
The high Tg copper-clad plate provided in this comparative example has the same composition and proportion as in example 2 except that no aluminum hydroxide was added, and the addition amount of aluminum hydroxide was entirely replaced with zinc borate, namely, 40 parts by weight of zinc borate was added; the preparation method is the same as that of the example 2;
and (3) testing: the high Tg copper clad laminate was taken out and tested according to each test method, and the test data were recorded as shown in Table 1.
Comparative example 3
The high Tg copper-clad plate provided in this comparative example has the same composition and proportion as in example 2 except that zinc borate is not added, and the added amount of zinc borate is replaced by aluminum hydroxide entirely, namely, 40 parts by weight of aluminum hydroxide is added; the preparation method is the same as that of the example 2;
and (3) testing: the high Tg copper clad laminate was taken out and tested according to each test method, and the test data were recorded as shown in Table 1.
Comparative example 4
The high Tg copper-clad plate provided in this comparative example has the same composition and proportion as in example 2, except that 30 parts of inorganic filler is added, and the preparation method is the same as in example 2;
and (3) testing: the high Tg copper clad laminate was taken out and tested according to each test method, and the test data were recorded as shown in Table 1.
Comparative example 5
The high Tg copper-clad plate provided in this comparative example has the same components and proportions as in example 2, except that the added inorganic filler is 65 parts, and the preparation method is the same as in example 2;
and (3) testing: the high Tg copper clad laminate was taken out and tested according to each test method, and the test data were recorded as shown in Table 1.
Comparative example 6
The high Tg copper-clad plate provided by the comparative example has the same components and proportions as those of the example 2, except that the total parts of the added aluminum hydroxide and zinc borate are 40 parts as those of the example 2, but the mass ratio of the aluminum hydroxide to the zinc borate is 9:1, and the preparation method is the same as that of the example 2;
and (3) testing: the high Tg copper clad laminate was taken out and tested according to each test method, and the test data were recorded as shown in Table 1.
Comparative example 7
The high Tg copper-clad plate provided by the comparative example has the same components and proportions as those of the example 2, except that the total parts of the added aluminum hydroxide and zinc borate are 40 parts as those of the example 2, but the mass ratio of the aluminum hydroxide to the zinc borate is 1:2, and the preparation method is the same as that of the example 2;
and (3) testing: the high Tg copper clad laminate was taken out and tested according to each test method, and the test data were recorded as shown in Table 1.
Comparative example 8
The high Tg copper clad laminate provided in this comparative example was substantially the same as example 2 in terms of the components and proportions, except that the brominated epoxy resin was replaced with bisphenol a epoxy resin (specifically, bisphenol epoxy resin of the model DFE1180 of east wood, its epoxy equivalent was 185), and the preparation method was the same as example 2;
and (3) testing: the high Tg copper clad laminate was taken out and tested according to each test method, and the test data were recorded as shown in Table 1.
The results of applying for performance testing to the Tg copper clad laminate prepared in examples 1 to 7 and comparative examples 1 to 8 are shown in Table 1, and specifically:
table 1 copper clad laminate various performance tests
As can be seen from the data in Table 1, the high Tg copper-clad plate provided by the application has excellent peeling strength, thermal stress, thermal delamination time and the like, and the glass transition temperature is effectively increased by more than 10 ℃ and CTI index can be effectively increased to more than 500V, even more than 600V by adding the inorganic filler mixture with a specific proportion into the base material consisting of the brominated epoxy resin and the dicyandiamide and then matching with other specific solvents and the curing accelerator; the data of comparative examples 2 and 1, 2 and 3 show that after adding inorganic filler mixture in specific proportion to the copper-clad plate, the glass transition temperature of the copper-clad plate is greatly improved compared with that of the copper-clad plate without adding or adding single filler, and the copper-clad plate has ultrahigh CTI value while providing the glass transition temperature, so that the zinc borate and aluminum hydroxide filler in the application has the effect of synergistically improving the Tg value and Comparative Tracking Index (CTI) of the copper-clad plate when being used in a brominated epoxy resin system; as can be seen from the data of comparative example 2 and comparative examples 3, 4, 5 and 6, the copper-clad plate has the effect of synergistically increasing the Tg value and the Comparative Tracking Index (CTI) of the copper-clad plate when the inorganic filler consisting of aluminum hydroxide and zinc borate in a specific ratio is added and the inorganic filler in a specific ratio is used in a brominated resin system; as can be seen from the data of example 2 and comparative example 8, the inorganic filler with a specific proportion in the copper-clad plate acts together with the epoxy resin with a specific type, and has the effects of synergistically improving the Tg value and the Comparative Tracking Index (CTI) of the copper-clad plate; in conclusion, the copper-clad plate can be applied to a printed circuit board, effectively improves the processability of the circuit board, and has good application effect.
The above embodiments are only for illustrating the technical solution of the present application, and are not limiting; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application, and are intended to be included within the scope of the appended claims and description.
Claims (10)
1. The high Tg copper-clad plate is characterized by comprising the following components in parts by weight: 350 to 450 parts of brominated epoxy resin, 7 to 10 parts of dicyandiamide, 0.1 to 0.25 part of curing accelerator, 70 to 90 parts of solvent, 35 to 60 parts of inorganic filler and 0.5 to 1 part of silane coupling agent.
2. The high Tg copper clad laminate of claim 1, comprising, in parts by weight: 380-420 parts of brominated epoxy resin, 7-9 parts of dicyandiamide, 0.1-0.2 part of curing accelerator, 75-85 parts of solvent, 48-55 parts of inorganic filler and 0.6-0.8 part of silane coupling agent.
3. The high Tg copper clad laminate of claim 1, comprising, in parts by weight: 400 parts of brominated epoxy resin, 8.6 parts of dicyandiamide, 0.17 part of a curing accelerator, 80 parts of a solvent, 40 parts of an inorganic filler and 0.7 part of a silane coupling agent.
4. The high Tg copper clad laminate of claim 1, wherein said cure accelerator is one or more of 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole.
5. The high Tg copper clad laminate of claim 4, wherein said solvent is one or more of dimethylformamide, acetone, methyl ethyl ketone.
6. The high Tg copper-clad laminate according to claim 4, wherein the inorganic filler is a mixture of zinc borate and aluminum hydroxide in a weight ratio of 1-3:3-8.
7. The high Tg copper clad laminate of claim 4, wherein said inorganic filler is zinc borate and aluminum hydroxide in parts by weight (2-3): 8, forming a mixture.
8. The high Tg copper clad laminate of claim 4, wherein said inorganic filler is a mixture of zinc borate and aluminum hydroxide in a weight ratio of 3:8.
9. The high Tg copper clad laminate of claim 4, wherein said zinc borate and aluminum hydroxide each have a particle size of 3 to 15 μm.
10. The method for producing a high Tg copper clad laminate according to any one of claims 1 to 9, comprising the steps of:
and (3) glue preparation: according to the formula requirement, mixing the solvent with the brominated epoxy resin, stirring, continuously adding dicyandiamide, a curing accelerator, an inorganic filler and a silane coupling agent after stirring uniformly, and stirring until the materials are completely dissolved to form a prepreg;
impregnation: pouring the presoaked liquid with the glue into an impregnation tank, impregnating the presoaked liquid with glass cloth, and baking the presoaked liquid for 3 to 10 minutes at the temperature of 160 to 220 ℃; and (3) superposing one or more layers of the baked glass cloth, coating copper foil on two sides of the superposed glass cloth, and laminating with 8-12 kraft paper at the temperature of 130-195 ℃ under the pressure of 0.4-3.7 MPa for 120-160 min to obtain the high Tg copper-clad plate.
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