CN111087762A - Fluorine-containing epoxy resin composite material and application thereof - Google Patents
Fluorine-containing epoxy resin composite material and application thereof Download PDFInfo
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- CN111087762A CN111087762A CN202010001062.XA CN202010001062A CN111087762A CN 111087762 A CN111087762 A CN 111087762A CN 202010001062 A CN202010001062 A CN 202010001062A CN 111087762 A CN111087762 A CN 111087762A
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- Prior art keywords
- epoxy resin
- fluorine
- parts
- containing epoxy
- composite material
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 233
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 233
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 182
- 239000011737 fluorine Substances 0.000 title claims abstract description 182
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 181
- 239000002131 composite material Substances 0.000 title claims abstract description 109
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000000945 filler Substances 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 78
- 239000011889 copper foil Substances 0.000 claims description 59
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims description 18
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000003825 pressing Methods 0.000 claims description 11
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 239000012779 reinforcing material Substances 0.000 claims description 8
- 239000011324 bead Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 239000004643 cyanate ester Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 2
- 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
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 claims description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002657 fibrous material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 150000008065 acid anhydrides Chemical class 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 description 31
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 28
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 28
- 239000012046 mixed solvent Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 22
- 229910052802 copper Inorganic materials 0.000 description 19
- 239000010949 copper Substances 0.000 description 19
- 238000002156 mixing Methods 0.000 description 17
- 239000004744 fabric Substances 0.000 description 16
- 239000003365 glass fiber Substances 0.000 description 15
- 150000008064 anhydrides Chemical class 0.000 description 14
- 239000003292 glue Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000003444 phase transfer catalyst Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 239000002274 desiccant Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 241000269435 Rana <genus> Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
Classifications
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- 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
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- 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
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- B32B2260/02—Composition of the impregnated, bonded or embedded layer
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- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/204—Di-electric
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/02—Polyglycidyl ethers of bis-phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2463/02—Polyglycidyl ethers of bis-phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to a fluorine-containing epoxy resin composite material and application thereof. The fluorine-containing epoxy resin composite material comprises the following raw materials: 40-120 parts of fluorine-containing epoxy resin; 40-100 parts of functional epoxy resin; 60-200 parts of a curing agent; 0.1-3 parts of a curing accelerator; 5-300 parts of a filler; the structural general formula of the fluorine-containing epoxy resin is shown as a formula (1), wherein n is an integer and is more than or equal to 1. The fluorine-containing epoxy resin and the functional epoxy resin are simultaneously used, the characteristics of the epoxy resin and the fluorine-containing modified epoxy resin are integrated, the dielectric property of the fluorine-containing epoxy resin composite material can be obviously improved, the adhesive property, the water resistance, the heat resistance and the like of the fluorine-containing epoxy resin composite material can be synergistically improved, and the prepared fluorine-containing epoxy resin composite material is low in dielectric constant, low in water absorption and good in adhesive property.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a fluorine-containing epoxy resin composite material and application thereof.
Background
With the development of wireless transmission products and high-frequency transmission technologies, electronic products are required to maintain good transmission quality, and phenomena such as attenuation, reflection and delay of signals are avoided. The dielectric constant of the material of the insulating layer in contact with the conductive line in the circuit board is an important factor influencing the impedance matching of high-frequency transmission, and the material of the insulating layer in contact with the conductive line in the circuit board needs a material with a lower dielectric constant in order to realize the impedance matching of high-frequency signal transmission.
As a material with excellent comprehensive performance, the epoxy resin has the advantages of excellent physical and mechanical properties, adhesive property, high chemical stability, low electrical insulation performance and shrinkage rate, easiness in processing and forming, low cost and the like. However, the dielectric properties of epoxy resins are poor, and the signal attenuation characteristics at high frequency cannot meet the strict requirements for high-frequency transmission, and cannot meet the requirements for high-order applications, especially for high-frequency printed circuit boards, so that the applications thereof are limited to a certain extent.
The fluorine-containing modified epoxy resin is prepared by introducing F into a resin structure, so that the polarity of the resin structure is reduced, the dielectric constant of the material is effectively reduced, and the material has excellent dielectric property; however, the fluorine-containing modified epoxy resin has poor mechanical properties and high cost, and the commercially available fluorine-containing epoxy resin is much more expensive than the epoxy resin, and the cost is up to several hundred yuan/kg, even thousands yuan/kg, so that the application of the fluorine-containing modified epoxy resin is limited.
Disclosure of Invention
In view of the above, it is necessary to provide a fluorine-containing epoxy resin composite material having good electronegativity, dielectric properties and mechanical properties.
The technical scheme is as follows:
the fluorine-containing epoxy resin composite material is prepared from the following raw materials in parts by weight:
40-120 parts of fluorine-containing epoxy resin; 40-100 parts of functional epoxy resin; 60-200 parts of a curing agent; 0.1-3 parts of a curing accelerator; 5-300 parts of a filler;
the structural general formula of the fluorine-containing epoxy resin is shown as the formula (1):
wherein n is an integer and n is more than or equal to 1.
The invention also provides a prepreg, and the raw material for preparing the prepreg comprises a reinforcing material and the fluorine-containing epoxy resin composite material.
The invention also provides a preparation method of the prepreg, which comprises the following steps:
impregnating or coating the fluorine-containing epoxy resin composite material into the reinforcing material, and curing.
The invention also provides a laminated board, and the preparation raw material of the laminated board comprises the prepreg.
The invention also provides a preparation method of the laminated board, which comprises the following steps:
laminating a plurality of said prepregs at a temperature of 200 ℃ under a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2 kPa.
The invention also provides a metal copper foil-clad laminated board, and the preparation raw materials of the metal copper foil-clad laminated board comprise a plurality of prepregs and metal copper foils.
The invention also provides a preparation method of the metal-clad copper foil laminated board, which is characterized by comprising the following steps:
superposing a plurality of prepregs to obtain a superposed body;
then pressing the metal copper foil on one side or two sides of the laminated body;
at a temperature of 200 ℃ and a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2 kPa.
Has the advantages that:
the fluorine-containing epoxy resin composite material is prepared by taking fluorine-containing modified epoxy resin as one of raw materials and matching with functional epoxy resin, a curing agent, a curing accelerator and a filler. The fluorine-containing epoxy resin composite material not only can fully exert the good adhesive property and mechanical property of the epoxy resin, but also can fully exert the excellent dielectric property of the fluorine-containing epoxy resin. In addition, the material has good heat resistance and low water absorption rate, and can be applied to high-frequency and high-speed products, such as high-frequency and high-power use environments with low signal loss, for example, high-power amplifiers of automobile anti-collision systems.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The fluorine-containing epoxy resin composite material is prepared from the following raw materials in parts by weight:
40-120 parts of fluorine-containing epoxy resin; 40-100 parts of functional epoxy resin; 60-200 parts of a curing agent; 0.1-3 parts of a curing accelerator; 5-300 parts of a filler;
the structural general formula of the fluorine-containing epoxy resin is shown as the formula (1):
wherein n is an integer and n is more than or equal to 1.
The electronegativity of fluorine is the highest of all elements, combined electrons are closer to a core, the interaction force between the electrons and the core is large, the bond energy of chemical bonds with other atoms is large, and the polarizability and the refractive index are low, so that the fluorine-containing polymer is endowed with excellent dielectric property and water resistance.
The fluorine-containing epoxy resin composite material is prepared by mixing fluorine-containing epoxy resin, functional epoxy resin, a curing agent, a curing accelerator and a filler, wherein the fluorine-containing epoxy resin contains fluorine, so that the polarity of a resin structure is reduced, the fluorine-containing epoxy resin and the functional epoxy resin are used simultaneously, the characteristics of the epoxy resin and the fluorine-containing modified epoxy resin are integrated, the dielectric property of the fluorine-containing epoxy resin composite material can be obviously improved, the cohesiveness, the water resistance and the heat resistance of the fluorine-containing epoxy resin composite material can be synergistically improved, and the prepared fluorine-containing epoxy resin composite material has the advantages of good electronegativity, lower dielectric constant, good dielectric property, low water absorption, good cohesiveness and good mechanical property.
The raw materials of the fluorine-containing epoxy resin composite material comprise 40-120 parts of fluorine-containing epoxy resin, preferably 50-110 parts of the fluorine-containing epoxy resin; further preferably, the fluorine-containing epoxy resin composition comprises 70-110 parts of the fluorine-containing epoxy resin; most preferably, 100 parts of the fluorine-containing epoxy resin is included.
The structural general formula of the epoxy resin is shown as a formula (1):
wherein n is an integer and n is more than or equal to 1.
The fluorine-containing epoxy resin has the advantages that F is introduced into the resin structure, so that the polarity of the resin structure is reduced, and the dielectric constant of the material can be effectively reduced.
The fluorine-containing epoxy resin is prepared from bisphenol AF and epichlorohydrin as raw materials under the action of an alkaline system and a phase transfer catalyst, and has the following main chemical equation:
the preparation method of the fluorine-containing epoxy resin comprises the following steps:
the molar ratio of the hexafluorobisphenol A to the epichlorohydrin is 1: 1-1: and 10, adding the phase transfer catalyst in an amount of 0.5-2% of the mole of the hexafluorobisphenol A, adding the bisphenol AF, the epichlorohydrin and the phase transfer catalyst into a reaction vessel, mixing and stirring, and reacting at the temperature of 65-75 ℃ for 65-70 hours to obtain a crude product of the fluorine-containing epoxy resin (DGEBF).
And (2) adding hot distilled water (the water temperature is 20-80 ℃) into the DGEBF crude product for washing, namely washing, extracting and layering, removing the phase transfer catalyst, then carrying out reduced pressure distillation in the vacuum degree of 400-1000 Pa to remove the extra solvent of the epoxy chloropropane, and finally adding sufficient drying agent for drying to obtain the fluorine-containing epoxy resin.
The phase transfer catalyst can be any one or mixture of more than two of benzyltriethylammonium chloride, trimethylbenzylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride and tetrabutylammonium chloride, and the mixture ratio of more than two is arbitrary.
The drying agent can be one or a mixture of anhydrous magnesium sulfate and anhydrous sodium sulfate.
The raw materials of the fluorine-containing epoxy resin composite material also comprise 40-100 parts of functional epoxy resin; preferably, 45-85 parts of the functional epoxy resin is included; further preferably, the functional epoxy resin comprises 50-80 parts of the functional epoxy resin; most preferably, 50 parts of the functional epoxy resin is included.
The functional epoxy resin is at least one selected from DCPD epoxy resin and biphenyl epoxy resin. By introducing the functional epoxy resin into the composition system, the toughness, the caking property, the heat resistance and the cost of the composition can be synergistically improved.
The raw materials of the fluorine-containing epoxy resin composite material also comprise 60-200 parts of a curing agent; preferably, 70-180 parts of the curing agent is included; further preferably, the curing agent comprises 90-150 parts; most preferably, 105 parts of the curing agent is included.
The curing agent is selected from at least one of cyanate ester curing agents and anhydride curing agents.
The raw materials of the fluorine-containing epoxy resin composite material also comprise 0.1-3 parts of a curing accelerator; preferably, 0.5-2.5 parts of the curing accelerator is included; further preferably, the curing accelerator comprises 0.6-2 parts; most preferably, 0.8 parts of the curing accelerator is included.
The curing accelerator is at least one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 1, 2-dimethylimidazole, 2-phenylimidazole and 2-phenyl-4-methylimidazole.
The raw materials of the fluorine-containing epoxy resin composite material also comprise 5-300 parts of filler; preferably, 10-250 parts of the filler is included; further preferably, the filler comprises 160-240 parts of the filler; most preferably, 240 parts of said filler is included.
The filler may be at least one selected from the group consisting of silica micropowder and hollow glass beads.
The invention also provides a prepreg, and the raw material for preparing the prepreg comprises a reinforcing material and the fluorine-containing epoxy resin composite material.
In some preferred embodiments, the reinforcing material is an inorganic or organic fibrous material.
In some more preferred embodiments, the reinforcement material is a low dielectric constant (3.8) quartz glass cloth, model 2116 glass fiber cloth (basis weight)105g/m2)。
The invention also provides a preparation method of the prepreg, which comprises the following steps:
impregnating or coating the fluorine-containing epoxy resin composite material into the reinforcing material, and curing.
The invention also provides a laminated board, and the preparation raw material of the laminated board comprises the prepreg.
The invention also provides a preparation method of the laminated board, which comprises the following steps:
laminating a plurality of said prepregs at a temperature of 200 ℃ under a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2 kPa.
The invention also provides a metal copper foil-clad laminated board, and the preparation raw materials of the metal copper foil-clad laminated board comprise a plurality of prepregs and metal copper foils.
In some more preferred embodiments, the metal copper foil is rtf copper foil.
The invention also provides a preparation method of the metal-clad copper foil laminated board, which is characterized by comprising the following steps:
superposing a plurality of prepregs to obtain a superposed body;
then pressing the metal copper foil on one side or two sides of the laminated body;
at a temperature of 200 ℃ and a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2 kPa.
The following are specific examples, and the main raw materials of the present invention are as follows:
the DCPD epoxy resin is available from Jiasheng, and has the model number of DPNE 1501;
the biphenyl type epoxy resin is available from Japan chemical, and the model is NC 3000;
bisphenol AF is available from Rana white pharmaceutical chemicals, and is of the type Lullaby;
epichlorohydrin can be purchased from Asahi morning chemical industry, and is epichlorohydrin;
the phase transfer catalyst benzyltrimethylammonium chloride is available from the creative chemical industry and is DMBAC;
cyanate ester is available from Switzerland, and has a model number of BA-3000S;
the anhydride curing agent can be purchased from Niulai and has the model of HN-2000 NT;
2-methylimidazole accelerators are available from basf as type 2 MI;
the silicon micropowder filler can be purchased from a great variety of sources, and the type is silicon micropowder;
hollow glass bead fillers are available from 3M in the united states, with the model being hollow glass beads.
Example 1
The present embodiment provides a fluorine-containing epoxy resin composite material, a prepreg, a laminate, and a metal-clad copper foil laminate.
(1) Preparing fluorine-containing epoxy resin: taking 7.6 parts of hexafluorobisphenol A, 42.3 parts of epichlorohydrin and 0.1 part of benzyl trimethyl ammonium chloride. Wherein the molar ratio of the hexafluorobisphenol A to the epichlorohydrin is 1: 10, the adding amount of benzyltrimethylammonium chloride is 1 percent of the mole of hexafluorobisphenol A.
Mixing the three sample materials, stirring, heating to 65-75 ℃, and reacting for 65-70 hours in the temperature range to obtain a fluorine-containing epoxy resin (DGEBF) crude product. Adding hot distilled water with the water temperature of 20-80 ℃ into the DGEBF crude product, carrying out water washing extraction layering, removing a phase transfer catalyst, then carrying out reduced pressure distillation to remove an extra solvent of epoxy chloropropane, and finally adding a sufficient amount of anhydrous magnesium sulfate drying agent for drying to obtain the fluorine-containing epoxy resin, wherein the yield is 80%.
(2) Preparing a fluorine-containing epoxy resin composite material: mixing cyclohexanone and propylene glycol methyl ether according to the volume ratio of 1:1 to obtain a mixed solvent, stirring, adding 40 parts of fluorine-containing epoxy resin, 40 parts of DCPD epoxy resin, 65 parts of anhydride curing agent, 0.8 part of 2-methylimidazole accelerator and 8 parts of silicon micropowder into the mixed solvent, and uniformly stirring to prepare a glue solution to obtain the fluorine-containing epoxy resin composite material 1.
(3) Preparing a prepreg: after the fluorine-containing epoxy resin composite material 1 was uniformly stirred, 2116 glass fiber cloth (basis weight 105 g/m)2) Impregnating fluorine-containing epoxy resin composite material, baking in an oven at 180 ℃ for 3min to obtain prepreg 1。
(4) Preparing a laminated board: superposing 8 sheets of the prepreg 1, and pressing the laminate at 200 ℃ and 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the laminated board 1.
(5) Preparing a metal copper foil-clad laminate: 8 sheets of the prepreg 1 were stacked, and a 36. mu. mRTF copper foil was stacked on both sides, and the stacked prepreg was heated at 200 ℃ under a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the metal-clad copper foil laminated board 1.
Example 2
The present embodiment provides a fluorine-containing epoxy resin composite material, a prepreg, a laminate, and a metal-clad copper foil laminate.
(1) The fluorine-containing epoxy resin obtained in example 1 was used as it is as the fluorine-containing epoxy resin of this example.
(2) Preparing a fluorine-containing epoxy resin composite material: mixing cyclohexanone and propylene glycol methyl ether according to the volume ratio of 1:1 to obtain a mixed solvent, stirring, adding 40 parts of fluorine-containing epoxy resin, 40 parts of DCPD DCPD epoxy resin, 65 parts of anhydride curing agent, 0.8 part of 2-methylimidazole accelerant and 150 parts of silicon micropowder into the mixed solvent, and uniformly stirring to prepare a glue solution, thereby obtaining the fluorine-containing epoxy resin composite material 2.
(3) Preparing a prepreg: after the fluorine-containing epoxy resin composite material 2 was uniformly stirred, 2116 glass fiber cloth (basis weight 105 g/m)2) Impregnating the fluorine-containing epoxy resin composite material, and baking in an oven at 180 ℃ for 3min to obtain a prepreg 2.
(4) Preparing a laminated board: superposing 8 sheets of the prepreg 2, and pressing the laminate at 200 ℃ and 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the laminated board 2.
(5) Preparing a metal copper foil-clad laminate: 8 sheets of the prepreg 2 were stacked, and a 36. mu. mRTF copper foil was stacked on both sides, and the stacked prepreg was heated at 200 ℃ under a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the metal-clad copper foil laminated board 2.
Example 3
The present embodiment provides a fluorine-containing epoxy resin composite material, a prepreg, a laminate, and a metal-clad copper foil laminate.
(1) The fluorine-containing epoxy resin obtained in example 1 was used as it is as the fluorine-containing epoxy resin of this example.
(2) Preparing a fluorine-containing epoxy resin composite material: mixing cyclohexanone and propylene glycol methyl ether according to the volume ratio of 1:1 to obtain a mixed solvent, stirring, adding 70 parts of fluorine-containing epoxy resin, 60 parts of biphenyl epoxy resin, 95 parts of anhydride curing agent, 1 part of 2-methylimidazole promoter and 160 parts of silica micropowder into the mixed solvent, and uniformly stirring to prepare a glue solution to obtain the fluorine-containing epoxy resin composite material 3.
(3) Preparing a prepreg: after the fluorine-containing epoxy resin composite material 3 was uniformly stirred, 2116 glass fiber cloth (basis weight 105 g/m)2) Impregnating the fluorine-containing epoxy resin composite material, and baking in an oven at 180 ℃ for 3min to obtain a prepreg 3.
(4) Preparing a laminated board: superposing 8 sheets of the prepreg 3, and heating the resultant laminate at 200 ℃ under a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the laminated board 3.
(5) Preparing a metal copper foil-clad laminate: 8 sheets of the prepreg 3 were stacked, and a 36. mu. mRTF copper foil was stacked on both sides, and the stacked prepreg was heated at 200 ℃ under a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the metal-clad copper foil laminated board 3.
Example 4
The present embodiment provides a fluorine-containing epoxy resin composite material, a prepreg, a laminate, and a metal-clad copper foil laminate.
(1) The fluorine-containing epoxy resin obtained in example 1 was used as it is as the fluorine-containing epoxy resin of this example.
(2) Preparing a fluorine-containing epoxy resin composite material: mixing cyclohexanone and propylene glycol methyl ether according to the volume ratio of 1:1 to obtain a mixed solvent, stirring, adding 80 parts of fluorine-containing epoxy resin, 70 parts of DCPD epoxy resin, 110 parts of anhydride curing agent, 0.6 part of 2-methylimidazole accelerator and 240 parts of silicon micropowder into the mixed solvent, and uniformly stirring to prepare a glue solution to obtain the fluorine-containing epoxy resin composite material 4.
(3) Preparing a prepreg: stirring the fluorine-containing epoxy resin composite material 4After homogenization, 2116 glass fiber cloth (basis weight 105 g/m)2) Impregnating the fluorine-containing epoxy resin composite material, and baking in an oven at 180 ℃ for 3min to obtain a prepreg 4.
(4) Preparing a laminated board: superposing 8 sheets of the prepreg 4, and heating the resultant laminate at 200 ℃ under a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the laminated board 4.
(5) Preparing a metal copper foil-clad laminate: 8 sheets of the prepreg 4 were stacked, and a 36. mu. mRTF copper foil was stacked on both sides, and the stacked prepreg was heated at 200 ℃ under a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the metal-clad copper foil laminated board 4.
Example 5
The present embodiment provides a fluorine-containing epoxy resin composite material, a prepreg, a laminate, and a metal-clad copper foil laminate.
(1) The fluorine-containing epoxy resin obtained in example 1 was used as it is as the fluorine-containing epoxy resin of this example.
(2) Preparing a fluorine-containing epoxy resin composite material: mixing cyclohexanone and propylene glycol methyl ether according to the volume ratio of 1:1 to obtain a mixed solvent, stirring, adding 80 parts of fluorine-containing epoxy resin, 70 parts of DCPD epoxy resin, 110 parts of anhydride curing agent, 0.6 part of 2-methylimidazole accelerator and 240 parts of hollow glass beads into the mixed solvent, and uniformly stirring to prepare a glue solution, thereby obtaining the fluorine-containing epoxy resin composite material 5.
(3) Preparing a prepreg: after the fluorine-containing epoxy resin composite material 4 was uniformly stirred, 2116 glass fiber cloth (basis weight 105 g/m)2) Impregnating the fluorine-containing epoxy resin composite material, and baking in an oven at 180 ℃ for 3min to obtain a prepreg 5.
(4) Preparing a laminated board: superposing 8 sheets of the prepreg 6, and pressing the laminate at 200 ℃ and 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the laminated board 5.
(5) Preparing a metal copper foil-clad laminate: 8 sheets of the prepreg 5 were stacked, and a 36. mu. mRTF copper foil was stacked on both sides, and the stacked prepreg was heated at 200 ℃ under a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the metal-clad copper foil laminated board 5.
Example 6
The present embodiment provides a fluorine-containing epoxy resin composite material, a prepreg, a laminate, and a metal-clad copper foil laminate.
(1) The fluorine-containing epoxy resin obtained in example 1 was used as it is as the fluorine-containing epoxy resin of this example.
(2) Preparing a fluorine-containing epoxy resin composite material: mixing cyclohexanone and propylene glycol methyl ether according to the volume ratio of 1:1 to obtain a mixed solvent, stirring, adding 70 parts of fluorine-containing epoxy resin, 60 parts of DCPD epoxy resin, 95 parts of anhydride curing agent, 1 part of 2-methylimidazole accelerator and 160 parts of silicon micropowder into the mixed solvent, and uniformly stirring to prepare a glue solution to obtain the fluorine-containing epoxy resin composite material 6.
(3) Preparing a prepreg: after the fluorine-containing epoxy resin composite material 6 was uniformly stirred, 2116 glass fiber cloth (basis weight 105 g/m)2) Impregnating the fluorine-containing epoxy resin composite material, and baking in an oven at 180 ℃ for 3min to obtain a prepreg 6.
(4) Preparing a laminated board: superposing 8 sheets of the prepreg 6, and pressing the laminate at 200 ℃ and 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the laminated board 6.
(5) Preparing a metal copper foil-clad laminate: 8 sheets of the prepreg 6 were stacked, and a 36. mu. mRTF copper foil was stacked on both sides, and the stacked prepreg was heated at 200 ℃ under a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the metal-clad copper foil laminated board 6.
Example 7
The present embodiment provides a fluorine-containing epoxy resin composite material, a prepreg, a laminate, and a metal-clad copper foil laminate.
(1) The fluorine-containing epoxy resin obtained in example 1 was used as it is as the fluorine-containing epoxy resin of this example.
(2) Preparing a fluorine-containing epoxy resin composite material: mixing cyclohexanone and propylene glycol methyl ether according to the volume ratio of 1:1 to obtain a mixed solvent, stirring, adding 100 parts of fluorine-containing epoxy resin, 50 parts of DCPD epoxy resin, 105 parts of anhydride curing agent, 0.8 part of 2-methylimidazole accelerator and 240 parts of silicon micropowder into the mixed solvent, and uniformly stirring to prepare a glue solution to obtain the fluorine-containing epoxy resin composite material 7.
(3) Preparing a prepreg: after the fluorine-containing epoxy resin composite material 7 was uniformly stirred, 2116 glass fiber cloth (basis weight 105 g/m)2) Impregnating the fluorine-containing epoxy resin composite material, and baking in an oven at 180 ℃ for 3min to obtain a prepreg 7.
(4) Preparing a laminated board: superposing 8 sheets of the prepreg 7, and heating the resultant laminate at 200 ℃ under a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the laminated board 7.
(5) Preparing a metal copper foil-clad laminate: 8 sheets of the prepreg 7 were stacked, and a 36. mu. mRTF copper foil was stacked on both sides, and the stacked prepreg was heated at 200 ℃ under a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the metal-clad copper foil laminated board 7.
Example 8
The present embodiment provides a fluorine-containing epoxy resin composite material, a prepreg, a laminate, and a metal-clad copper foil laminate.
(1) The fluorine-containing epoxy resin obtained in example 1 was used as it is as the fluorine-containing epoxy resin of this example.
(2) Preparing a fluorine-containing epoxy resin composite material: mixing cyclohexanone and propylene glycol methyl ether according to the volume ratio of 1:1 to obtain a mixed solvent, stirring, adding 70 parts of fluorine-containing epoxy resin, 60 parts of DCPD epoxy resin, 150 parts of anhydride curing agent, 2 parts of 2-methylimidazole accelerator and 240 parts of silicon micropowder into the mixed solvent, and uniformly stirring to prepare a glue solution to obtain the fluorine-containing epoxy resin composite material 8.
(3) Preparing a prepreg: after the fluorine-containing epoxy resin composite material 8 was uniformly stirred, 2116 glass fiber cloth (basis weight 105 g/m)2) Impregnating the fluorine-containing epoxy resin composite material, and baking in an oven at 180 ℃ for 3min to obtain the prepreg 8.
(4) Preparing a laminated board: superposing 8 sheets of the prepreg 8, and pressing the laminate at 200 ℃ and 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the laminated board 8.
(5) Preparing a metal copper foil-clad laminate: superposing 8 sheets of the prepreg 8, and laminating 36. mu. mRTF copper foil on each side, and heating200 ℃ under a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the metal-clad copper foil laminated board 8.
Example 9
The present embodiment provides a fluorine-containing epoxy resin composite material, a prepreg, a laminate, and a metal-clad copper foil laminate.
(1) The fluorine-containing epoxy resin obtained in example 1 was used as it is as the fluorine-containing epoxy resin of this example.
(2) Preparing a fluorine-containing epoxy resin composite material: mixing cyclohexanone and propylene glycol methyl ether according to the volume ratio of 1:1 to obtain a mixed solvent, stirring, adding 105 parts of fluorine-containing epoxy resin, 70 parts of DCPD epoxy resin, 200 parts of cyanate ester, 2 parts of 2-methylimidazole accelerant and 300 parts of hollow glass beads into the mixed solvent, and uniformly stirring to prepare a glue solution to obtain the fluorine-containing epoxy resin composite material 9.
(3) Preparing a prepreg: after the fluorine-containing epoxy resin composite material 9 was uniformly stirred, 2116 glass fiber cloth (basis weight 105 g/m)2) Impregnating the fluorine-containing epoxy resin composite material, and baking in an oven at 180 ℃ for 3min to obtain the prepreg 9.
(4) Preparing a laminated board: superposing 8 sheets of the prepreg 9, and heating the resultant laminate at 200 ℃ under a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the laminated board 9.
(5) Preparing a metal copper foil-clad laminate: 8 sheets of the prepreg 9 were stacked, and a 36. mu. mRTF copper foil was stacked on both sides, and the stacked prepreg was heated at 200 ℃ under a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the metal-clad copper foil laminated board 9.
Comparative example 1
The present comparative example provides an epoxy resin composite, a prepreg, a laminate, and a metal-clad copper foil laminate.
(1) Preparing an epoxy resin composite material: mixing cyclohexanone and propylene glycol methyl ether according to the volume ratio of 1:1 to obtain a mixed solvent, stirring, adding 130 parts of DCPD epoxy resin, 95 parts of anhydride curing agent, 1 part of 2-methylimidazole accelerant and 160 parts of silica micropowder into the mixed solvent, and uniformly stirring to prepare a glue solution to obtain the epoxy resin composite material 10.
(2) Preparing a prepreg: after the epoxy resin composite material 10 was uniformly stirred, 2116 glass fiber cloth (basis weight 105 g/m)2) Impregnating the fluorine-containing epoxy resin composite material, and baking in an oven at 180 ℃ for 3min to obtain the prepreg 10.
(3) Preparing a laminated board: superposing 8 sheets of the prepreg 10, and pressing the laminate at 200 ℃ and 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the laminated board 10.
(4) Preparing a metal copper foil-clad laminate: 8 sheets of the prepreg 10 were stacked, and a 36. mu. mRTF copper foil was stacked on both sides, and the stacked prepreg was heated at 200 ℃ under a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the metal-clad copper foil laminated board 10.
Comparative example 2
The present comparative example provides an epoxy resin composite, a prepreg, a laminate, and a metal-clad copper foil laminate.
(1) Preparing an epoxy resin composite material: mixing cyclohexanone and propylene glycol methyl ether according to the volume ratio of 1:1 to obtain a mixed solvent, stirring, adding 105 parts of fluorine-containing epoxy resin-1, 70 parts of DCPD epoxy resin, 200 parts of cyanate ester, 2 parts of 2-methylimidazole accelerator and 300 parts of hollow glass beads into the mixed solvent, and uniformly stirring to prepare a glue solution, thereby obtaining the fluorine-containing epoxy resin composite material 11.
(2) Preparing a prepreg: after the epoxy resin composite material 10 was uniformly stirred, 2116 glass fiber cloth (basis weight 105 g/m)2) Impregnating the fluorine-containing epoxy resin composite material, and baking in an oven at 180 ℃ for 3min to obtain the prepreg 11.
(3) Preparing a laminated board: superposing 8 sheets of the prepreg 11, and heating the resultant laminate at 200 ℃ under a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the laminated board 11.
(4) Preparing a metal copper foil-clad laminate: 8 sheets of the prepreg 11 were stacked, and a 36. mu. mRTF copper foil was stacked on both sides, and the stacked prepreg was heated at 200 ℃ under a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the metal-clad copper foil laminated board 11.
The fluorine-containing epoxy resin-1 has the following chemical formula:
the synthesis and performance of the fluorine-containing epoxy resin-1 are referred to in the literature [ Zhang Chun Ling, Nahui, Liu Guo zong, et al.
Comparative example 3
The present comparative example provides a fluorine-containing epoxy resin composite, a prepreg, a laminate, and a metal-clad copper foil laminate.
(1) The fluorine-containing epoxy resin obtained in example 1 was directly used as the fluorine-containing epoxy resin of this comparative example.
(2) Preparing a fluorine-containing epoxy resin composite material: mixing cyclohexanone and propylene glycol methyl ether according to the volume ratio of 1:1 to obtain a mixed solvent, stirring, adding 30 parts of fluorine-containing epoxy resin, 130 parts of DCPD epoxy resin, 50 parts of anhydride curing agent, 5 parts of 2-methylimidazole accelerator and 240 parts of silicon micropowder into the mixed solvent, and uniformly stirring to prepare a glue solution to obtain the fluorine-containing epoxy resin composite material 12.
(3) Preparing a prepreg: after the fluorine-containing epoxy resin composite material 12 was uniformly stirred, 2116 glass fiber cloth (basis weight 105 g/m)2) Impregnating the fluorine-containing epoxy resin composite material, and baking in an oven at 180 ℃ for 3min to obtain the prepreg 12.
(4) Preparing a laminated board: superposing 8 sheets of the prepreg 12, and pressing the same at 200 ℃ and 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the laminated board 12.
(5) Preparing a metal copper foil-clad laminate: 8 sheets of the prepreg 12 were stacked, and a 36. mu. mRTF copper foil was stacked on both sides, and the stacked prepreg was heated at 200 ℃ under a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the metal-clad copper foil laminated board 12.
Comparative example 4
The present comparative example provides a fluorine-containing epoxy resin composite, a prepreg, a laminate, and a metal-clad copper foil laminate.
(1) The fluorine-containing epoxy resin obtained in example 1 was directly used as the fluorine-containing epoxy resin of this comparative example.
(2) Preparing a fluorine-containing epoxy resin composite material: mixing cyclohexanone and propylene glycol methyl ether according to a volume ratio of 1:1 to obtain a mixed solvent, stirring, adding 100 parts of fluorine-containing epoxy resin, 50 parts of bisphenol A epoxy resin, 105 parts of anhydride curing agent, 0.8 part of 2-methylimidazole accelerator and 240 parts of silicon micropowder into the mixed solvent, and uniformly stirring to prepare a glue solution to obtain the fluorine-containing epoxy resin composite material 13.
(3) Preparing a prepreg: after the fluorine-containing epoxy resin composite material 13 was uniformly stirred, 2116 glass fiber cloth (basis weight 105 g/m)2) Impregnating the fluorine-containing epoxy resin composite material, and baking the impregnated composite material in an oven at 180 ℃ for 3min to obtain the prepreg 13.
(4) Preparing a laminated board: 8 sheets of the prepreg 13 were stacked, and the stacked prepreg was heated at 200 ℃ under a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the laminated board 13.
(5) Preparing a metal copper foil-clad laminate: 8 sheets of the prepreg 13 were stacked, and a 36. mu. mRTF copper foil was stacked on both sides, and the stacked prepreg was heated at 200 ℃ under a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the metal-clad copper foil laminated board 13.
Comparative example 5
The present comparative example provides a fluorine-containing epoxy resin composite, a prepreg, a laminate, and a metal-clad copper foil laminate.
(1) The fluorine-containing epoxy resin obtained in example 1 was directly used as the fluorine-containing epoxy resin of this comparative example.
(2) Preparing a fluorine-containing epoxy resin composite material: mixing cyclohexanone and propylene glycol methyl ether according to the volume ratio of 1:1 to obtain a mixed solvent, stirring, adding 130 parts of fluorine-containing epoxy resin, 95 parts of anhydride curing agent, 1 part of 2-methylimidazole accelerant and 160 parts of silica micropowder into the mixed solvent, and uniformly stirring to prepare a glue solution to obtain the fluorine-containing epoxy resin composite material 14.
(3) Preparing a prepreg: after the fluorine-containing epoxy resin composite material 14 was uniformly stirred, 2116 glass fiber cloth (basis weight 105 g/m)2) Fluorine-containing epoxy resin impregnated composite materialThe prepreg material was baked in an oven at 180 ℃ for 3min to obtain a prepreg 14.
(4) Preparing a laminated board: superposing 8 sheets of the prepreg 14, and pressing the same at 200 ℃ and 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the laminated board 14.
(5) Preparing a metal copper foil-clad laminate: 8 sheets of the prepreg 14 were stacked, and a 36. mu. mRTF copper foil was stacked on both sides, and the stacked prepreg was heated at 200 ℃ under a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2kPa to obtain the metal-clad copper foil laminated board 14.
The compositions of the fluorine-containing epoxy resin composite materials in examples 1 to 9 and comparative examples 1 to 5 are shown in Table 1.
TABLE 1
Performance tests were conducted on the metal-clad copper foil laminates 1 to 14 obtained in examples 1 to 9 and comparative examples 1 to 5.
Physical properties of the copper foil substrates manufactured in the respective examples and comparative examples were evaluated according to the following methods:
1. evaluation of peel strength: and testing the peeling strength between the copper foil and the circuit carrier plate. The peel strength was measured by the peel strength test method specified in test IPC-TM-6502.4.8.
2. Evaluation of bending Strength: and testing the bending strength of the optical plate after the metal covering layer of the circuit carrier plate is completely removed. The test was carried out according to the bending strength test method specified in IPC-TM-6502.4.4.
3. Evaluation of Heat resistance: the samples with copper plates were placed in a tin furnace at 288 ℃ using the wicking method and the time for the samples to explode and delaminate was recorded.
4. DK/DF evaluation: the Dielectric constant DK and the loss factor DF at a frequency of 1GHz were measured with a Dielectric Analyzer (Dielectric Analyzer) HP Agilent E4991A. The test was carried out according to the DK/DF test method as specified by IPC-TM-6502.5.5.9.
5. Water absorption evaluation: the weight change before and after heating was calculated after heating the sample in a pressure cooker of 120 ℃ and 2atm for 120 minutes. The water absorption was measured according to the water absorption test method specified in IPC-TM-6502.6.2.1. The test results of the metal-clad copper foil laminates 1 to 20 are shown in table 2:
TABLE 2
As can be seen from table 1, the excellent properties of the fluorine-containing epoxy resin, the functional epoxy resin, and the like are fully combined in examples 1 to 9, and the metal-clad copper foil laminated plates prepared by adjusting the respective proportions have good dielectric properties (dielectric constant (1GHz) < 3.5; dielectric loss (1GHz) <0.006), and the metal-clad copper foil laminated plates prepared in examples 1 to 9 have good heat resistance, peel strength, flexural strength, and low water absorption.
The metal-clad copper foil laminated plates prepared in the comparative examples 1 to 5 are obviously inferior to the examples in comprehensive performance. In the comparative example 1, no fluorine-containing epoxy resin is added, but DCPD epoxy resin is used completely, the dielectric property of the prepared copper-clad plate is poor, and the requirement of the dielectric property of a high-frequency substrate material cannot be met; in the comparative example 2, if the added fluorine-containing epoxy resin is not the fluorine-containing epoxy resin, the prepared copper-clad plate has poor mechanical property and dielectric property; in comparative example 3, the amount of the fluorine-containing epoxy resin is too small, the amount of the DCPD epoxy resin is too large, and the dielectric property of the product is poor; comparative example 4 no functional epoxy resin was used, and laminates prepared using a conventional bisphenol a epoxy resin instead of a DCPD epoxy resin had poor dielectric properties; comparative example 5, in which no functional epoxy resin was added and only fluorine-containing epoxy resin was used, the cost was increased, and the laminate produced therefrom was low in peel strength and poor in flexural strength.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (15)
1. The fluorine-containing epoxy resin composite material is characterized by being prepared from the following raw materials in parts by weight:
40-120 parts of fluorine-containing epoxy resin; 40-100 parts of functional epoxy resin; 60-200 parts of a curing agent; 0.1-3 parts of a curing accelerator; 5-300 parts of a filler;
the structural general formula of the fluorine-containing epoxy resin is shown as the formula (1):
wherein n is an integer and n is more than or equal to 1.
2. The fluorine-containing epoxy resin composite material according to claim 1, which is prepared from the following raw materials in parts by weight:
50-110 parts of fluorine-containing epoxy resin; 45-85 parts of functional epoxy resin; 70-180 parts of a curing agent; 0.5-2.5 parts of a curing accelerator; 10-250 parts of a filler.
3. The fluorine-containing epoxy resin composite material according to claim 1, which is prepared from the following raw materials in parts by weight:
70-110 parts of fluorine-containing epoxy resin; 50-80 parts of functional epoxy resin; 90-150 parts of a curing agent; 0.6-2 parts of a curing accelerator; 160-240 parts of a filler.
4. The fluorine-containing epoxy resin composite material according to claim 1, which is prepared from the following raw materials in parts by weight:
100 parts of fluorine-containing epoxy resin; 50 parts of functional epoxy resin; 105 parts of a curing agent; 0.8 part of curing accelerator; 240 parts of filler.
5. The fluorine-containing epoxy resin composite material according to any one of claims 1 to 4, wherein the functional epoxy resin is at least one selected from DCPD epoxy resin and biphenyl type epoxy resin.
6. The fluorine-containing epoxy resin composite material according to any one of claims 1 to 4, wherein the curing agent is at least one selected from cyanate ester curing agents and acid anhydride curing agents.
7. The fluorine-containing epoxy resin composite material according to any one of claims 1 to 4, wherein the curing accelerator is at least one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 1, 2-dimethylimidazole, 2-phenylimidazole and 2-phenyl-4-methylimidazole.
8. The fluorine-containing epoxy resin composite material according to any one of claims 1 to 4, wherein the filler is at least one selected from the group consisting of fine silica powder and hollow glass beads.
9. A prepreg, characterized in that a raw material for producing the prepreg comprises a reinforcing material and the fluorine-containing epoxy resin composite material according to any one of claims 1 to 8.
10. The prepreg of claim 9, wherein the reinforcing material is an inorganic or organic fibrous material.
11. A method of producing a prepreg according to claim 9 or 10, comprising the steps of:
and (3) impregnating or coating the fluorine-containing epoxy resin composite material into the reinforcing material, and curing.
12. A laminate characterized in that it is prepared from a stock comprising a prepreg according to claim 7 or 8.
13. A method of making the laminate of claim 12, comprising the steps of:
laminating a plurality of said prepregs at a temperature of 200 ℃ under a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2 kPa.
14. A metal-copper-clad laminate characterized in that a raw material for producing the metal-copper-clad laminate comprises a plurality of the prepregs according to claim 9 or 10, and a metal copper foil.
15. A method of making the metal-clad laminate of claim 14, comprising the steps of:
superposing a plurality of prepregs to obtain a superposed body;
then pressing the metal copper foil on one side or two sides of the laminated body;
at a temperature of 200 ℃ and a pressure of 25kgf/cm2And hot-press forming for 120min under the condition that the vacuum degree is less than 2 kPa.
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