CN115028963B - Resin composition and manufacturing method of high-Tg low-Dk/Df high-frequency copper-clad plate - Google Patents
Resin composition and manufacturing method of high-Tg low-Dk/Df high-frequency copper-clad plate Download PDFInfo
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- CN115028963B CN115028963B CN202210825202.4A CN202210825202A CN115028963B CN 115028963 B CN115028963 B CN 115028963B CN 202210825202 A CN202210825202 A CN 202210825202A CN 115028963 B CN115028963 B CN 115028963B
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- 239000011342 resin composition Substances 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000003822 epoxy resin Substances 0.000 claims abstract description 41
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 41
- 150000002148 esters Chemical class 0.000 claims abstract description 21
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 20
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 10
- 239000004305 biphenyl Substances 0.000 claims abstract description 10
- 239000013032 Hydrocarbon resin Substances 0.000 claims abstract description 8
- 229920006270 hydrocarbon resin Polymers 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000011256 inorganic filler Substances 0.000 claims abstract description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims description 38
- 239000011347 resin Substances 0.000 claims description 38
- 239000003063 flame retardant Substances 0.000 claims description 14
- 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 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000003292 glue Substances 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- 239000011889 copper foil Substances 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 7
- 238000007731 hot pressing Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 6
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- -1 ester modified bisphenol F Chemical class 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims 2
- 230000009477 glass transition Effects 0.000 abstract description 8
- 230000032798 delamination Effects 0.000 abstract description 4
- 230000026030 halogenation Effects 0.000 abstract description 2
- 238000005658 halogenation reaction Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920013638 modified polyphenyl ether Polymers 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- 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
- B32B27/38—Layered products comprising a layer 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
Abstract
The invention discloses a resin composition and a method for manufacturing a high-Tg low-Dk/Df high-frequency copper-clad plate, wherein the resin composition comprises the following components in parts by weight: 25-45 parts of biphenyl type epoxy resin, 10-15 parts of active ester modified epoxy resin, 20-30 parts of bisphenol A type epoxy resin, 50-60 parts of active ester curing agent, 5-7 parts of hydrocarbon resin, 0.1-0.33 part of curing agent accelerator, 30-45 parts of inorganic filler and 20-40 parts of solvent. The copper-clad plate pressed by the process has good dielectric property, glass transition temperature (Tg is more than or equal to 200 ℃), low expansion coefficient, thermal delamination time (T288) of more than 60min, low dielectric constant/dielectric loss (DK is less than or equal to 3.8 and DF is less than or equal to 0.005), no halogenation and can be basically applied to the manufacture of high-Tg low-Dk/Df high-frequency copper-clad plates.
Description
Technical Field
The invention belongs to the technical field of copper-clad plates, and particularly relates to a resin composition and a manufacturing method of a high-Tg low-Dk/Df high-frequency copper-clad plate.
Background
In recent years, with the development of downstream communication, consumer electronics, automobile electronics and other industries, the demand of various electronic products for copper-clad plates is greatly increased, and the development space and market scale of the copper-clad plate industry are further widened. With the acceleration of the 5G commercial process, the investment scale of the communication field is obviously improved, the development of world electronic information industry represented by artificial intelligence AI and the like is more and more advanced, high-tech electronic products become one of the most potential industries in the world today, meanwhile, the requirements for high-frequency copper-clad plates are more and more increased, and the dielectric constant (DK) and dielectric Dissipation Factor (DF) become two important performance indexes applied to the field of the high-frequency copper-clad plates.
At present, the flame-retardant product is mostly more than 90% in the production of the epoxy resin copper-clad plate, and the flame retardance must reach V-0 grade in view of safety, the user needs that the product must pass UL safety certification. Some foreign research institutions propose that halogen flame retardants can produce toxic substances during combustion, which are harmful to human health and pollute the environment. The international and European, especially, european, concerns about this problem, and the European Commission on environmental protection (EC) has proposed a limited period of use of halogen-containing flame retardant materials in electric and electronic products, and the development of halogen-free flame retardant copper-clad plates has become an important subject in the industry.
The glass transition temperature (Tg) refers to the temperature at which the glass transitions to a high elastic state. The glass transition is inherent property of amorphous polymer material, is macro-expression of the transformation of the polymer movement form, directly affects the service performance and the technological performance of the copper-clad plate, and is the main content of the research and development of the high-frequency copper-clad plate for a long time. At present, in the printed circuit board industry, the TG values of most halogen-free copper-clad plates are about 150 ℃, the dielectric constant (DK) >4.2 and the dielectric loss (DF) >0.12, and the copper-clad plates of the type are not suitable for manufacturing high-frequency copper-clad plates.
Disclosure of Invention
According to the defects of the prior art, the invention aims to provide a resin composition and a manufacturing method of a high-Tg low-Dk/Df high-frequency copper-clad plate, wherein the copper-clad plate has good dielectric property and glass transition temperature), low expansion coefficient and low dielectric constant/dielectric loss, and can be basically applied to manufacturing of the high-Tg low-Dk/Df high-frequency copper-clad plate.
In order to achieve the above purpose, the technical scheme adopted is as follows:
the invention aims at providing a resin composition which comprises the following components in parts by weight:
further, the biphenyl type epoxy resin has the following structural formula:
the main chain of the biphenyl type epoxy resin contains biphenyl groups which are high-rigidity heat-resistant groups, the structure of almost plane biphenyl groups increases the regularity of chains and acting force among molecules, physical crosslinking density is increased in isotropic grids, and the cured product has good heat resistance and higher Tg transition temperature.
Preferably, the bisphenol A epoxy resin is formed by reacting bisphenol A and epichlorohydrin in the presence of sodium hydroxide, and has the structural formula:
typically, the low relative molecular mass epoxy resin has an n average value of less than 2 and a softening point of less than 50 ℃, also known as a soft epoxy resin; the n value of the epoxy resin with medium relative molecular mass is between 2 and 5, and the softening point is between 50 and 95 ℃; and resins with n greater than 5 (softening point above 100 ℃) are known as high relative molecular mass resins. Wherein n is generally between 0 and 25.
Preferably, the curing agent accelerator is at least one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and DMAP. The catalyst is used as a catalyst in the present invention.
Preferably, the solvent is at least one of acetone, butanone, xylene, propylene glycol monomethyl ether and cyclohexanone.
Preferably, the inorganic filler is at least one of aluminum hydroxide, magnesium hydroxide, nitrogen flame retardant, phosphorus flame retardant, antimony trioxide, talcum powder, silicon micropowder and titanium dioxide.
Preferably, the Active Ester modified epoxy resin is a mixture of bisphenol F type epoxy resin and bisphenol A type epoxy resin modified by Active Ester (Active Ester) functional groups, wherein the molar ratio of the Active Ester modified bisphenol F type epoxy resin to the Active Ester modified bisphenol A type epoxy resin is 1:1. bisphenol F type epoxy resin and bisphenol A type epoxy resin with good electrical property are adopted in the main structure, and active ester groups are introduced into the structure, so that the main structure can obtain reliable chemical stability, impact resistance, electrical property (Dk/Df), heat resistance and the like.
Preferably, the classical structural formula of the hydrocarbon resin is as follows:
wherein n is 5 to 20.
The presence of polar groups is an important factor in the high order of the materials Dk and Df. In general, the more polar groups, the higher Dk and Df, whereas the lower the polar groups, the smaller Dk and Df. The active ester used in the method meets the index requirements of low water absorption and low Dk/Df, can be used as a curing agent of epoxy resin, and can greatly reduce the specific gravity of polar groups in the resin, thereby reducing Dk and Df of the resin and further achieving the purpose of improving dielectric properties.
Preferably, the active ester curing agent is HPC-8000-65T, but not limited thereto.
The second object of the invention is to provide a method for manufacturing a high-Tg low Dk/Df high-frequency copper-clad plate, which comprises the resin composition, and comprises the following steps:
(1) Dissolving ring-modified polyphenyl ether resin, alkylphenol novolac epoxy resin, bisphenol A epoxy resin, an active ester curing agent, a curing agent accelerator, an inorganic filler in a solvent, emulsifying and dispersing, and simultaneously preparing the whole system to control the content of resin glue in a certain range until the emulsification and the dispersion are uniform for 2 hours, and stopping stirring to obtain resin glue solution;
(2) Impregnating the resin glue solution prepared in the step (1) on glass fiber cloth, and baking for 3-10 minutes in a baking oven at 160-170 ℃ to obtain a bonding sheet;
(3) Laminating the bonding sheets in step (2), coating 12-35 μm copper foil on one or both sides, placing between stainless steel plates, and placing in a vacuum press at 10-35 kg/cm 2 And hot-pressing for 120-180 minutes at 170-220 ℃ to obtain the copper-clad plate.
Preferably, the gel time of the resin glue solution obtained in the step (1) is 200-390 seconds (171 ℃), and the solid content is 55-70%.
Preferably, the resin fluidity of the adhesive sheet in the step (2) is 15-35%, the resin gel content is 40-70%, and the gel time is 140-190 seconds (171 ℃).
Compared with the prior art, the invention has the beneficial effects that:
the copper-clad plate obtained by pressing through the process has good dielectric property, glass transition temperature (Tg is more than or equal to 200 ℃), low expansion coefficient, thermal delamination time (T288) of more than 60min, low dielectric constant/dielectric loss (DK is less than or equal to 3.8 and DF is less than or equal to 0.005), no halogenation, and can be basically applied to manufacturing high-frequency copper-clad plates with high Tg and low Dk/Df.
Detailed Description
The invention is described below in connection with examples which are given solely for the purpose of illustration and are not intended to limit the scope of the invention.
"parts" in the following examples are in parts by weight.
Example 1
35 parts of biphenyl type epoxy resin (170-190 g/eq) and 20 parts of bisphenol A type epoxy resin (180-260 g/eq) are taken, 10 parts of active ester modified epoxy resin, 56 parts of active ester curing agent, 7 parts of hydrocarbon resin, 0.21 part of DMAP, 15 parts of silica micropowder, 10 parts of magnesium hydroxide and 10 parts of nitrogen flame retardant, and a proper amount of 10 parts of acetone, 10 parts of cyclohexanone and 20 parts of dimethylbenzene are added as solvents to prepare a resin solution with the solid content of 64% under full stirring.
The resin solution is soaked in 2116 glass fiber cloth, and baked at 170 ℃ for 7 minutes to prepare the bonding sheet. The content of the adhesive sheet resin was 55.+ -. 5% and the fluidity of the resin was 25.+ -. 4%.
6 bonding sheets are taken, laminated in order, coated with 18 mu m copper foil on both sides, placed between stainless steel plates, then placed in a vacuum press, and heated at 175+/-3 ℃ at 35kg/cm 2 And hot-pressing for 180 minutes under the condition to prepare the double-sided copper-clad plate.
Example 2
25 parts of biphenyl type epoxy resin (the epoxy equivalent weight is 170-190 g/eq), 30 parts of bisphenol A type epoxy resin (the epoxy equivalent weight is 180-260 g/eq), 50 parts of active ester curing agent, 15 parts of active ester modified epoxy resin, 5 parts of hydrocarbon resin, 0.21 part of DMAP, 0.1 part of 2-methylimidazole, 15 parts of silicon micropowder, 10 parts of antimony trioxide and 10 parts of phosphorus flame retardant, and a proper amount of 10 parts of butanone, 10 parts of dimethylbenzene and 10 parts of methylbenzene are added as solvents, and the mixture is fully stirred to prepare a resin solution with the solid content of 64%.
The resin solution is soaked in 7628 glass fiber cloth, and baked for 9 minutes at 170 ℃ to prepare the bonding sheet. The content of the adhesive sheet resin was 55.+ -. 5% and the fluidity of the resin was 25.+ -. 4%.
6 bonding sheets are taken, laminated in order, coated with 18 mu m copper foil on both sides, placed between stainless steel plates, then placed in a vacuum press, and heated at 175+/-3 ℃ at 35kg/cm 2 And hot-pressing for 180 minutes under the condition to prepare the double-sided copper-clad plate.
Example 3
45 parts of biphenyl type epoxy resin (170-190 g/eq) and 26 parts of bisphenol A type epoxy resin (180-260 g/eq) are taken, 50 parts of active ester curing agent, 10 parts of active ester modified epoxy resin, 6 parts of hydrocarbon resin, 0.21 part of 2-ethyl-4-methylimidazole, 0.1 part of 2-methylimidazole, 15 parts of nitrogen flame retardant, 10 parts of titanium dioxide and 10 parts of phosphorus flame retardant are added, and a proper amount of 15 parts of butanone, 10 parts of dimethylbenzene, 10 parts of toluene and 5 parts of propylene glycol monomethyl ether are added as solvents to prepare a resin solution with the solid content of 64% under full stirring.
The resin solution is soaked in 2116 glass fiber cloth, and baked at 170 ℃ for 6 minutes to prepare the bonding sheet. The content of the adhesive sheet resin was 55.+ -. 5% and the fluidity of the resin was 25.+ -. 4%.
6 bonding sheets are taken, laminated in order, coated with 18 mu m copper foil on both sides, placed between stainless steel plates, then placed in a vacuum press, and heated at 175+/-3 ℃ at 35kg/cm 2 And hot-pressing for 180 minutes under the condition to prepare the double-sided copper-clad plate.
Comparative example 1
33 parts of benzoxazine type epoxy resin, 18 parts of phenol-aralkyl epoxy resin, 33 parts of active ester curing agent, 0.30 part of 2-ethylimidazole, 20 parts of antimonous oxide and 8 parts of aluminum hydroxide are taken, 5 parts of acetone and 35 parts of toluene are added as solvents, and resin solution with the solid content of 65% is prepared under sufficient stirring.
The resin solution was impregnated with glass cloth model numbers 7628 and 2116, and baked at 170℃for 9 minutes to prepare a bonding sheet. The content of the adhesive sheet resin was 55.+ -. 3%, and the fluidity of the resin was 21.+ -. 3%.
6 bonding sheets are taken, laminated in order, coated with 18 mu m copper foil on both sides, placed between stainless steel plates, then placed in a vacuum press, and heated at 220+ -3deg.C and 40kg/cm 2 And hot-pressing for 180 minutes under the condition to prepare the double-sided copper-clad plate.
Comparative example 2
40 parts of biphenyl type epoxy resin, 21 parts of phenol-aralkyl epoxy resin, 10 parts of o-cresol type phenolic epoxy resin, 0.21 part of imidazole, 15 parts of silicon micropowder, 10 parts of nitrogen flame retardant and 10 parts of magnesium hydroxide, and 15 parts of acetone and 20 parts of propylene glycol monomethyl ether are added as solvents, and the mixture is fully stirred to prepare a resin solution with 65% of solid content.
The resin solution was impregnated with 7628 and 2116 glass fiber cloth, and baked at 170℃for 7 minutes to prepare a bonding sheet. The content of the adhesive sheet resin was 55.+ -. 4%, and the fluidity of the resin was 25.+ -. 4%.
6 bonding sheets are taken, laminated in order, coated with 18 mu m copper foil on both sides, placed between stainless steel plates, then placed in a vacuum press, and heated at 220+ -3deg.C and 40kg/cm 2 And hot-pressing for 120 minutes under the condition to prepare the double-sided copper-clad plate.
Comparative example 3
Comparative example 3 differs from example 1 in that a mixture of bisphenol F type epoxy resin and bisphenol a type epoxy resin, which has not been modified with an active ester, was used.
Testing
The following tests were carried out on the double-sided copper-clad plates prepared in examples 1 to 3 and comparative examples 1 to 2:
(1) Glass transition temperature (Tg) and Thermal Mechanical Analysis (TMA) was used as the test method
(2) Coefficient of Thermal Expansion (CTE), testing methods employ thermomechanical analysis (TMA)
(3) Thermal decomposition temperature (Td), test method using thermogravimetric analysis (TGA)
(4) Flammability as measured by the UL94 vertical Combustion method in the united states
(5) Thermal delamination time (T288), test method using thermomechanical analysis (TMA)
(6) Peel strength, test method measured according to IPC-TM-650.2.4.9
(7) Dielectric constant (Dk) and dielectric loss (Df), measured according to ASTM-D150 and IPC-TM-6502.5.5.9
(8) Processability test method was measured according to IPC-TM-650.2.4.7
(9) Dip soldering resistance test method IPC-TM-650.2.6.8 measurement
The results obtained from the test are shown in Table 1.
TABLE 1 data comparison of double-sided copper-clad plates of examples 1 to 3 and comparative examples 1 to 2
As can be seen from the test data in Table 1, compared with comparative examples 1 to 3, the copper-clad plate prepared from the resin composition of examples 1 to 3 has excellent comprehensive properties such as high glass transition temperature (Tg is more than or equal to 200 ℃), high heat resistance, low dielectric constant and dielectric loss, thermal delamination time (T288) >60min, good dielectric properties and the like, meets the halogen-free flame retardant requirement, has good processability, and is basically suitable for preparing a high-Tg low Dk/Df high-frequency copper-clad plate.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (8)
1. The resin composition is characterized by comprising the following components in parts by weight:
25-45 parts of biphenyl type epoxy resin
10-15 parts of active ester modified epoxy resin
20-30 parts of bisphenol A type epoxy resin
50-60 parts of active ester curing agent
5-7 parts of hydrocarbon resin
0.1 to 0.33 part of curing agent accelerator
30-45 parts of inorganic filler
20-40 parts of a solvent;
the structural formula of the hydrocarbon resin is as follows:
；
wherein n is 5 to 20;
the active ester modified epoxy resin is a mixture of bisphenol F epoxy resin and bisphenol A epoxy resin which are modified by adopting an active ester functional group, wherein the mole ratio of the active ester modified bisphenol F epoxy resin to the active ester modified bisphenol A epoxy resin is 1:1.
2. the resin composition of claim 1, wherein the biphenyl epoxy resin has the structural formula:
。
3. the resin composition of claim 1, wherein the bisphenol a epoxy resin is produced by reacting bisphenol a and epichlorohydrin in the presence of sodium hydroxide, and has the structural formula:
；
wherein n is 0 to 25.
4. The resin composition according to claim 1, wherein the curing agent accelerator is at least one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and DMAP.
5. The resin composition according to claim 1, wherein the solvent is at least one of acetone, butanone, xylene, propylene glycol monomethyl ether, and cyclohexanone; the inorganic filler is at least one of aluminum hydroxide, magnesium hydroxide, nitrogen flame retardant, phosphorus flame retardant, antimony trioxide, talcum powder, silicon micropowder and titanium dioxide.
6. A method for manufacturing a high-Tg, low-Dk/Df high-frequency copper-clad plate, comprising the resin composition of any one of claims 1 to 5, comprising the steps of:
(1) Dissolving biphenyl type epoxy resin, active ester modified epoxy resin, bisphenol A type epoxy resin, an active ester curing agent, hydrocarbon resin, a curing agent accelerator, an inorganic filler in a solvent, emulsifying and dispersing, and simultaneously preparing the whole system to control the content of resin glue in a certain range until the resin glue is uniformly emulsified and dispersed for 2 hours, and stopping stirring to obtain resin glue solution;
(2) Impregnating the resin glue solution prepared in the step (1) on glass fiber cloth, and baking for 3-10 minutes in a 160-170 ℃ baking oven to obtain a bonding sheet;
(3) Laminating the bonding sheets in the step (2), coating 12-35 μm copper foil on one or both sides, placing between stainless steel plates, and placing in a vacuum press at 10-35 kg/cm 2 And hot-pressing for 120-180 minutes at 170-220 ℃ to obtain the copper-clad plate.
7. The method of claim 6, wherein the resin glue solution obtained in the step (1) has a gel time of 200 to 390 seconds (171 ℃) and a solid content of 55 to 70%.
8. The method according to claim 6, wherein the adhesive sheet in step (2) has a resin fluidity of 15 to 35%, a resin gel content of 40 to 70%, and a gel time of 140 to 190 seconds (171 ℃).
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