CN114133703A - Preparation method of halogen-free low-dielectric compatible high-frequency FR4 copper-clad plate - Google Patents
Preparation method of halogen-free low-dielectric compatible high-frequency FR4 copper-clad plate Download PDFInfo
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- CN114133703A CN114133703A CN202111541617.0A CN202111541617A CN114133703A CN 114133703 A CN114133703 A CN 114133703A CN 202111541617 A CN202111541617 A CN 202111541617A CN 114133703 A CN114133703 A CN 114133703A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003292 glue Substances 0.000 claims abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 31
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000007822 coupling agent Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000000539 dimer Substances 0.000 claims abstract description 14
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 13
- 239000003822 epoxy resin Substances 0.000 claims abstract description 12
- -1 glycidyl ester Chemical class 0.000 claims abstract description 12
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 12
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 11
- 239000004744 fabric Substances 0.000 claims abstract description 11
- 239000003365 glass fiber Substances 0.000 claims abstract description 11
- 229920002545 silicone oil Polymers 0.000 claims abstract description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 9
- 239000011889 copper foil Substances 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 8
- 239000010445 mica Substances 0.000 claims abstract description 8
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005011 phenolic resin Substances 0.000 claims abstract description 7
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000008096 xylene Substances 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 7
- 229920003986 novolac Polymers 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 4
- 239000004743 Polypropylene Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007731 hot pressing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- KGSFMPRFQVLGTJ-UHFFFAOYSA-N 1,1,2-triphenylethylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 KGSFMPRFQVLGTJ-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
- C08L63/10—Epoxy resins modified by unsaturated 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
- B32B15/085—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 polyolefins
-
- 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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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)
- Laminated Bodies (AREA)
Abstract
The invention belongs to the technical field of copper-clad plates, and particularly relates to a preparation method of a halogen-free low-dielectric compatible high-frequency FR4 copper-clad plate. According to the invention, bio-based dimer acid glycidyl ester modified polyfunctional alicyclic epoxy resin is used as main resin, and vinyl-terminated silicone oil, BT resin and linear phenolic resin are added to improve the resin proportion, so that the dielectric loss is reduced while the thermosetting property is increased; adding a dimethylbenzene solvent, a titanate coupling agent, a platinum catalyst, a CYC solvent, imidazole, dimethylformamide graphene nano-particles, aluminum hydroxide, aluminum oxide and mica powder, and completely dissolving and emulsifying to obtain a glue solution; completely soaking the obtained glue solution into ne glass fiber cloth, and forming PP through certain process treatment; covering PP with copper foil, and performing a certain pressing process to obtain the copper-clad plate with the dielectric constant of 3.8-3.9, the dielectric loss (10G) of 0.005-0.007, the Tg of more than 200 ℃, the T of more than 288 minutes, the flame retardance reaching FV-0 grade and the water absorption of less than 0.10 percent.
Description
Technical Field
The invention belongs to the technical field of copper-clad plates, and particularly relates to a preparation method of a halogen-free low-dielectric compatible high-frequency FR4 copper-clad plate.
Background
At present, a large number of flame-retardant copper-clad plates contain halides, antimonides and the like, the copper-clad plates of the type have unpleasant smell and release hydrogen halide gas with high toxicity and strong corrosivity when being ignited and combusted, and bromine flame retardants can generate dioxin with carcinogenic effect when being combusted, so that the bromine flame retardants harm human health and pollute the environment. The demand for using halogen and the like in copper-clad plates is higher and higher internationally, and simultaneously, halogen-free environmental protection instructions of European Union are responded, so that the development of halogen-free copper-clad plates and the improvement of other performances are urgently needed.
The civil high-frequency communication is greatly developed and widely applied to the fields of remote communication, navigation, medical treatment, transportation, traffic and the like, the mobile phone, the wireless communication and the automobile phone are developed to high frequency due to high transmission quality and high confidentiality, the use frequency is shifted from MHz to GHz, the high frequency and high speed of electronic products have higher requirements on the high frequency characteristic of the printed board, and the high-frequency copper-clad plate is more required by the market.
In order to protect the environment and meet the high-frequency and high-speed characteristics, it is imperative to develop a halogen-free low-dielectric compatible high-frequency copper-clad plate.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a halogen-free low-dielectric compatible high-frequency FR4 copper-clad plate, which adopts component materials different from the existing copper-clad plate, uses bio-based dimer acid glycidyl ester modified polyfunctional alicyclic epoxy resin as main resin, adds vinyl-terminated silicone oil, BT resin and linear phenolic resin to improve the resin proportion, increases thermosetting property, reduces medium loss, and further solves the problems of environmental pollution caused by halide, dielectric loss and high-frequency compatibility.
A preparation method of a halogen-free low-dielectric compatible high-frequency FR4 copper-clad plate comprises the steps of using glue liquid components in the preparation process to comprise resin, a coupling agent, a catalyst, a filler and a solvent, wherein the resin takes a biological-based dimer acid glycidyl ester modified polyfunctional alicyclic epoxy resin as main resin.
Further, the resin also comprises BT resin, vinyl-terminated silicone oil and linear phenolic resin.
The beneficial effect who adopts above-mentioned scheme is: the invention has different components from the components of the existing halogen-free low-dielectric compatible high-frequency copper-clad plate on the market in the glue solution of the copper-clad plate, uses the bio-based dimer acid glycidyl ester modified polyfunctional alicyclic epoxy resin as the main resin, adds the vinyl-terminated silicone oil, the BT resin and the linear phenolic resin to improve the resin proportion, increases the thermosetting property, reduces the dielectric loss and solves the problems of environmental pollution, dielectric loss and high-frequency compatibility of halides at the same time.
Further, the coupling agent is a titanate coupling agent, and the catalyst comprises a platinum catalyst and imidazole.
Further, the filler comprises aluminum hydroxide, dimethylformamide graphene nanoparticles, aluminum oxide and mica powder, and the solvent comprises xylene and cyclohexanone (CYC).
The beneficial effect who adopts above-mentioned scheme is: the invention adopts the novel resin, the novel coupling agent, the catalyst, the solvent and the filler for proportioning, and provides another possibility for preparing the halogen-free low-dielectric compatible high-frequency copper-clad plate.
Further, the preparation method of the halogen-free low-dielectric compatible high-frequency FR4 copper-clad plate comprises the following steps:
(1) at normal temperature, adding 30-50 parts by weight of bio-based dimer acid glycidyl ester modified polyfunctional alicyclic epoxy resin, 11-25 parts by weight of BT resin, 3-7 parts by weight of vinyl-terminated silicone oil, 13-30 parts by weight of linear phenolic resin, 0.3-0.9 part by weight of titanate coupling agent and 77-103 parts by weight of cyclohexanone solvent into a container, and stirring to fully dissolve the materials;
(2) at normal temperature, adding 0.09-0.12 part by weight of imidazole and 0.15-0.27 part by weight of platinum catalyst into the mixed solution obtained in the step (1), and stirring to fully dissolve the imidazole and the platinum catalyst;
(3) adding 15-17 parts by weight of aluminum hydroxide, 8-9 parts by weight of dimethylformamide graphene nanoparticles, 57-69 parts by weight of aluminum oxide and 14-20 parts by weight of mica powder into the mixed solution obtained in the step (2), uniformly stirring and fully emulsifying;
(4) adding 10-20 parts by weight of xylene solvent and 10-20 parts by weight of cyclohexanone solvent into the mixed solution obtained in the step (3) to adjust the viscosity and uniformly stirring to obtain glue solution;
(5) completely and uniformly soaking the ne glass fiber cloth in the glue solution obtained in the step (4), and processing to obtain PP;
(6) and (4) laminating the PP covering copper foil prepared in the step (5) to obtain the halogen-free low-dielectric compatible high-frequency FR4 copper-clad plate.
Further, in the steps (1) - (4), the glue solution is uniform and stable, the gelling time of the glue solution is 240-400 s, the viscosity is 15-30 Pa.s.
Further, in the step (5), uniformly distributing the glue solution on the ne glass fiber cloth, and baking for 4-10 min by using an oven at 145-190 ℃ to obtain PP; the PP is uniform in appearance, the fluidity is 13-15%, and the gel content is 40-65%.
Further, in the step (6), the obtained PP is overlapped, copper foil covers two surfaces of the PP, and the PP is hot-pressed for 2-5 hours at the temperature of 160-210 ℃ and the pressure of 7-35 MPa in a vacuum press for 1-2 hours to obtain the halogen-free low-dielectric compatible high-frequency FR4 copper-clad plate.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, bio-based dimer acid glycidyl ester modified polyfunctional alicyclic epoxy resin is used as main resin, and vinyl-terminated silicone oil, BT resin and linear phenolic resin are added to improve the resin proportion, so that the dielectric loss is reduced while the thermosetting property is increased;
(2) the invention is different from the components of the existing halogen-free low-dielectric compatible high-frequency copper-clad plate on the market in the glue solution component of the copper-clad plate, adopts a novel resin, a novel coupling agent, a catalyst bonding solvent and a filler for proportioning, and provides another possibility for the preparation of the halogen-free low-dielectric compatible high-frequency copper-clad plate;
(3) the copper-clad plate provided by the invention has the dielectric constant of 3.8-3.9, the dielectric loss (10G) of 0.005-0.007, the Tg of more than 200 ℃, the T288 of more than 120 minutes, the flame retardance reaching FV-0 level and the water absorption rate of less than 0.10%.
Detailed Description
The principles and features of this invention are described below in conjunction with examples, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
A preparation method of a halogen-free low-dielectric compatible high-frequency FR4 copper-clad plate comprises the following steps:
(1) at normal temperature, 30 parts by weight of bio-based dimer acid glycidyl ester modified polyfunctional alicyclic epoxy resin (HXION Vast-Sen (original shell) dimer acid diglycidyl ester modifier HELOXY 71), 11 parts by weight of BT resin, 3 parts by weight of vinyl-terminated silicone oil, 13 parts by weight of phenol-formaldehyde novolac resin, 0.3 part by weight of titanate coupling agent and 77 parts by weight of CYC solvent are added into a container and stirred to be fully dissolved;
(2) at normal temperature, adding 0.09 part of imidazole and 0.15 part of platinum catalyst in parts by weight into the mixed solution obtained in the step (1), and stirring to fully dissolve the imidazole and the platinum catalyst;
(3) adding 15 parts by weight of aluminum hydroxide, 8 parts by weight of dimethylformamide graphene nanoparticles, 57 parts by weight of alumina and 14 parts by weight of mica powder into the mixed solution obtained in the step (2), uniformly stirring and fully emulsifying;
(4) adding 10 parts by weight of xylene solvent and 13 parts by weight of CYC solvent into the mixed solution obtained in the step (3) to adjust the viscosity, and uniformly stirring to obtain a glue solution, wherein the glue solution has a gelling time of 323s and a viscosity of 17Pa.s, and is uniform and stable;
(5) completely and uniformly soaking the ne glass fiber cloth in the glue solution obtained in the step (4), and baking the ne glass fiber cloth in an oven at 175 ℃ for 7min to obtain PP with uniform appearance, 13% of controlled fluidity and 49% of glue content;
(6) and (3) overlapping 2 PP prepared in the step (5) according to the requirement, covering 18-micron copper foil on two surfaces, hot-pressing for 4 hours at the temperature of 160-210 ℃ in a vacuum press under the pressure of 7-35 MPa for 2 hours, and preserving heat for 2 hours to obtain the halogen-free low-dielectric compatible high-frequency FR4 copper-clad plate.
Example 2
A preparation method of a halogen-free low-dielectric compatible high-frequency FR4 copper-clad plate comprises the following steps:
(1) at normal temperature, 40 parts by weight of bio-based dimer acid glycidyl ester modified polyfunctional alicyclic epoxy resin (HXION Vast-Sen (original shell) dimer acid diglycidyl ester modifier HELOXY 71), 17 parts by weight of BT resin, 5 parts by weight of vinyl-terminated silicone oil, 23 parts by weight of phenol-formaldehyde novolac resin, 0.5 part by weight of titanate coupling agent and 85 parts by weight of CYC solvent are added into a container and stirred to be fully dissolved;
(2) at normal temperature, adding 0.1 part of imidazole and 0.21 part of platinum catalyst in parts by weight into the mixed solution in the step (1), and stirring to fully dissolve the imidazole and the platinum catalyst;
(3) adding 16 parts by weight of aluminum hydroxide, 8.5 parts by weight of dimethylformamide graphene nanoparticles, 63 parts by weight of aluminum oxide and 16 parts by weight of mica powder into the mixed solution obtained in the step (2), uniformly stirring, and fully emulsifying;
(4) adding 15 parts of xylene solvent and 16 parts of CYC solvent into the mixed solution obtained in the step (3) in parts by weight to adjust the viscosity, and uniformly stirring to obtain a glue solution, wherein the glue solution has a gelling time of 354 seconds and a viscosity of 26Pa.s, and is uniform and stable;
(5) baking the ne glass fiber cloth completely and uniformly soaked by the glue solution obtained in the step (4) for 5min by a 185 ℃ oven to obtain PP with uniform appearance, 14% of controlled fluidity and 55% of glue content;
(6) and (3) overlapping 4 pieces of PP prepared in the step (5) according to the requirement, covering 18-micron copper foils on two sides, hot-pressing for 5 hours at the temperature of 160-210 ℃ in a vacuum press under the pressure of 7-35 MPa for 2 hours, and preserving heat for 2 hours to obtain the halogen-free low-dielectric compatible high-frequency FR4 copper-clad plate.
Example 3
A preparation method of a halogen-free low-dielectric compatible high-frequency FR4 copper-clad plate comprises the following steps:
(1) at normal temperature, 50 parts by weight of bio-based dimer acid glycidyl ester modified multifunctional alicyclic epoxy resin (HXION Vast-Sasen (original shell) dimer acid diglycidyl ester modifier HELOXY 71), 25 parts by weight of BT resin, 7 parts by weight of vinyl-terminated silicone oil, 30 parts by weight of phenol-formaldehyde linear resin, 0.9 part by weight of titanate coupling agent and 103 parts by weight of CYC solvent are added into a container and stirred to be fully dissolved;
(2) at normal temperature, adding 0.12 part of imidazole and 0.27 part of platinum catalyst in parts by weight into the mixed solution in the step (1), and stirring to fully dissolve the imidazole and the platinum catalyst;
(3) adding 17 parts by weight of aluminum hydroxide, 9 parts by weight of dimethylformamide graphene nanoparticles, 69 parts by weight of alumina and 20 parts by weight of mica powder into the mixed solution obtained in the step (2), uniformly stirring and fully emulsifying;
(4) adding 20 parts of xylene solvent and 19 parts of CYC solvent into the mixed solution obtained in the step (3) in parts by weight, adjusting the viscosity, and uniformly stirring to obtain a glue solution, wherein the glue solution has a gelling time of 297s and a viscosity of 25Pa.s, and is uniform and stable;
(5) baking the ne glass fiber cloth completely and uniformly soaked by the glue solution obtained in the step (4) for 4min by using a 165 ℃ oven to obtain PP with uniform appearance, 14% of controlled fluidity and 60% of glue content;
(6) and (3) overlapping 6 pieces of PP prepared in the step (5) according to the requirement, covering 18-micron copper foil on two sides, hot-pressing for 5 hours at the temperature of 160-210 ℃ in a vacuum press under the pressure of 7-35 MPa for 2 hours, and preserving heat for 2 hours to obtain the halogen-free low-dielectric compatible high-frequency FR4 copper-clad plate.
Comparative example
A preparation method of a halogen-free copper-clad plate comprises the following steps:
(1) weighing the glue solution components in parts by weight: 13 parts of tetraphenylethane resin, 15 parts of phenolic novolac resin, 12 parts of phosphorus-containing epoxy resin, 0.9 part of KH-560 coupling agent, 103 parts of CYC solvent, 50 parts of xylene solvent, 0.03 part of imidazole and 55 parts of aluminum hydroxide filler, and fully mixing and stirring uniformly to obtain a glue solution;
(2) completely and uniformly soaking the ne glass fiber cloth in the glue solution obtained in the step (1), and baking the ne glass fiber cloth in an oven at 200 ℃ for 5min to obtain 55% of PP (polypropylene) glue content;
(3) and (3) overlapping 2 PP sheets prepared in the step (2) according to the requirement, covering 18-micron copper foil on two surfaces, and hot-pressing in a vacuum press at the temperature of 150 ℃ for 1.5h under the pressure of 3MPa to obtain the halogen-free copper-clad plate.
Description of the test methods:
(1) dielectric constant: GB/T4722-2017-8.5;
(2) dielectric loss (10G): GB/T4722-2017-8.5;
(3)Tg(DSC)：GB/T 4722-2017-6.7.1；
(4)T288：GB/T 4722-2017-6.11；
(5) peel strength (N/mm): GB/T4722-2017.2.1;
(6) flame retardancy: GB/T4722-2017-6.4.1;
(7)(Cl+Br)PPM：GB/T 4722-2017-6.3；
(8) water absorption (%): GB/T4722-20179.2.
The test data of each example and comparative example are shown in table 1.
TABLE 1 data of test experiments for examples and comparative examples
| Test items | Example 1 | Example 2 | Example 3 | Comparative example |
| Dielectric constant | 3.80 | 3.82 | 3.85 | 4.21 |
| Dielectric loss (10G) | 0.0062 | 0.0063 | 0.0064 | 0.011 |
| Tg(DSC)/℃ | 219 | 214 | 207 | 183 |
| T288/min | >120 | >120 | >120 | 60 |
| Peel strength N/mm | 1.67 | 1.65 | 1.60 | 1.33 |
| Flame retardancy | FV-0 | FV-0 | FV-0 | FV-0 |
| (Cl+Br)PPM | <500 | <500 | <500 | <500 |
| Water absorption (%) | 0.08 | 0.08 | 0.08 | 0.12 |
By comparing test experimental data in the table 1, the copper-clad plate of the embodiment has the dielectric constant of 3.8-3.9, the dielectric loss (10G) of 0.005-0.007, the Tg of more than 200 ℃, the T288 of more than 120 minutes, the flame retardance reaching FV-0 grade and the water absorption of less than 0.10 percent.
Compared with comparative example 1, the dielectric constant, dielectric loss, Tg and other indexes of examples 1-3 are obviously improved, and other basic indexes of examples 1-3 are better than those of comparative example 1. Therefore, compared with the existing halogen-free copper-clad plate, the novel copper-clad plate has lower dielectric constant, low loss and compatible high frequency, and other indexes are not reduced.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. The preparation method of the halogen-free low-dielectric compatible high-frequency FR4 copper-clad plate is characterized in that glue solution components used in the preparation process comprise resin, a coupling agent, a catalyst, a filler and a solvent, wherein the resin takes bio-based dimer acid glycidyl ester modified polyfunctional alicyclic epoxy resin as main resin.
2. The method of claim 1, wherein the resin further comprises BT resin, vinyl terminated silicone oil and phenol novolac resin.
3. The method of claim 1, wherein the coupling agent is a titanate coupling agent and the catalyst comprises a platinum catalyst and an imidazole.
4. The method according to claim 1, wherein the filler comprises aluminum hydroxide, dimethylformamide graphene nanoparticles, aluminum oxide and mica powder, and the solvent comprises xylene and cyclohexanone.
5. The method according to claim 1 to 4, comprising the steps of:
(1) adding 30-50 parts by weight of bio-based dimer acid glycidyl ester modified polyfunctional alicyclic epoxy resin, 11-25 parts by weight of BT resin, 3-7 parts by weight of vinyl-terminated silicone oil, 13-30 parts by weight of linear phenolic resin, 0.3-0.9 part by weight of titanate coupling agent and 77-103 parts by weight of cyclohexanone solvent into a container, and stirring to fully dissolve the materials;
(2) adding 0.09-0.12 part of imidazole and 0.15-0.27 part of platinum catalyst in parts by weight into the mixed solution obtained in the step (1), and stirring to fully dissolve the imidazole and the platinum catalyst;
(3) adding 15-17 parts by weight of aluminum hydroxide, 8-9 parts by weight of dimethylformamide graphene nanoparticles, 57-69 parts by weight of aluminum oxide and 14-20 parts by weight of mica powder into the mixed solution obtained in the step (2), uniformly stirring and fully emulsifying;
(4) adding 10-20 parts by weight of xylene solvent and 10-20 parts by weight of cyclohexanone solvent into the mixed solution obtained in the step (3) to adjust the viscosity and uniformly stirring to obtain glue solution;
(5) completely and uniformly soaking the ne glass fiber cloth in the glue solution obtained in the step (4), and processing to obtain PP;
(6) and (4) laminating the PP covering copper foil prepared in the step (5) to obtain the halogen-free low-dielectric compatible high-frequency FR4 copper-clad plate.
6. The preparation method according to claim 5, wherein in the steps (1) to (4), the gel time of the glue solution is 240-400 s, the viscosity is 15-30 Pa.s, and the glue solution is uniform and stable.
7. The preparation method according to claim 5, wherein in the step (5), the glue solution is uniformly distributed on the ne glass fiber cloth, and the obtained mixture is baked in an oven at 145-190 ℃ for 4-10 min to obtain PP.
8. The preparation method according to claim 7, wherein the PP has a uniform appearance, a fluidity of 13-15% and a gel content of 40-65%.
9. The preparation method according to claim 5, characterized in that in the step (6), the obtained PP is overlapped, copper foil covers two surfaces of the PP, and the PP is hot-pressed for 2-5 h at the temperature of 160-210 ℃ and the pressure of 7-35 MPa in a vacuum press for 1-2 h, so that the halogen-free low-dielectric compatible high-frequency FR4 copper-clad plate is obtained.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115339191A (en) * | 2022-08-15 | 2022-11-15 | 黄河三角洲京博化工研究院有限公司 | Para-aramid paper composite base halogen-free low-dielectric copper-clad plate and preparation method thereof |
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| CN106739289A (en) * | 2016-11-26 | 2017-05-31 | 山东金宝科创股份有限公司 | A kind of preparation method of Halogen, High Tg CCL |
| CN111500249A (en) * | 2020-05-20 | 2020-08-07 | 山东金宝电子股份有限公司 | Low-dielectric-property low-water-absorption halogen-free copper-clad plate and preparation method thereof |
| CN111793327A (en) * | 2020-07-08 | 2020-10-20 | 山东金宝电子股份有限公司 | Epoxy resin composition for high-speed high-frequency copper-clad plate and preparation method thereof |
| CN112048155A (en) * | 2020-09-18 | 2020-12-08 | 林州致远电子科技有限公司 | Glue solution for halogen-free medium-Tg loss copper-clad plate and preparation method and application thereof |
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Patent Citations (4)
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| CN106739289A (en) * | 2016-11-26 | 2017-05-31 | 山东金宝科创股份有限公司 | A kind of preparation method of Halogen, High Tg CCL |
| CN111500249A (en) * | 2020-05-20 | 2020-08-07 | 山东金宝电子股份有限公司 | Low-dielectric-property low-water-absorption halogen-free copper-clad plate and preparation method thereof |
| CN111793327A (en) * | 2020-07-08 | 2020-10-20 | 山东金宝电子股份有限公司 | Epoxy resin composition for high-speed high-frequency copper-clad plate and preparation method thereof |
| CN112048155A (en) * | 2020-09-18 | 2020-12-08 | 林州致远电子科技有限公司 | Glue solution for halogen-free medium-Tg loss copper-clad plate and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115339191A (en) * | 2022-08-15 | 2022-11-15 | 黄河三角洲京博化工研究院有限公司 | Para-aramid paper composite base halogen-free low-dielectric copper-clad plate and preparation method thereof |
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