CN108485182B - High-frequency resin composition and prepreg and laminated board manufactured by using same - Google Patents
High-frequency resin composition and prepreg and laminated board manufactured by using same Download PDFInfo
- Publication number
- CN108485182B CN108485182B CN201810253291.3A CN201810253291A CN108485182B CN 108485182 B CN108485182 B CN 108485182B CN 201810253291 A CN201810253291 A CN 201810253291A CN 108485182 B CN108485182 B CN 108485182B
- Authority
- CN
- China
- Prior art keywords
- parts
- epoxy resin
- resin composition
- resin
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
-
- 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
- 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
-
- 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
- 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
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
-
- 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
- B32B2363/00—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
- B32B2386/00—Specific polymers obtained by polycondensation or polyaddition not provided for in a single one of index codes B32B2363/00 - B32B2383/00
-
- 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
- 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
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2361/04, C08J2361/18, and C08J2361/20
-
- 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
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2461/04, C08J2461/18, and C08J2461/20
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Abstract
The invention discloses a high-frequency resin composition, which comprises the following components in parts by weight: (A) fluorine-containing benzoxazine prepolymer: 20-100 parts of a solvent; (B) epoxy resin: 0-80 parts; (C) curing agent: 0-30 parts of a solvent; (D) flame retardant: 0-30 parts of a solvent; (E) accelerator (b): 0 to 10 parts. The fluorine-containing benzoxazine prepolymer is adopted, and the benzoxazine ring structure prepolymer material reduces the concentration of hydroxyl groups generated during curing in the prior art, relatively improves the content of benzene rings, and greatly reduces the dielectric constant and the dielectric loss of products; meanwhile, the fluorine-containing benzoxazine prepolymer has a large number of hydrogen bond acting bodies, so that the problems of difficult forming process, poor cohesiveness, poor toughness, poor mechanical property and the like caused by the fact that a little polar groups are used in a polytetrafluoroethylene technology applied to a printed circuit laminated board in the prior art are solved.
Description
Technical Field
The invention relates to a high-frequency resin composition, and a prepreg and a laminated board prepared from the high-frequency resin composition, and belongs to the technical field of electronic materials.
Background
With the development of communication and electronic products towards high frequency and high speed, users have higher and higher performance requirements on the products, high-frequency high-performance substrate materials have become important leading-edge technologies for the development of printed circuit board industries, and more enterprises are added to the development of new copper-clad plate new materials. The traditional resin substrate material is replaced by a high-frequency, high-speed and high-reliability substrate material, and the market demand is increasing. The performance of high-frequency microwave circuit boards directly determines the high frequency, high speed, high reliability, and the like of high-end electronic information technology.
Because Polytetrafluoroethylene (PTFE) has excellent microwave performance, chemical stability and low water absorption, the application is wide, the change of dielectric constant and dielectric loss factor is small under high frequency, and the polytetrafluoroethylene resin becomes one of important materials of a high-end high-frequency copper-clad plate. However, polytetrafluoroethylene has its own disadvantages that limit its application: the surface is inert, so that the activation is difficult, the combination with the copper foil is difficult, and the adhesion is poor; the glass transition temperature (Tg) is low, the thermal expansion is large, and the yield of fine circuit processing is very low; and insufficient mechanical properties, such as low tensile strength and modulus and low hardness of PTFE.
In the prior art, in order to meet the requirements of low dielectric constant, low dielectric loss and high moisture and heat resistance, Chinese patent application CN102558858A discloses a resin composition for a high-frequency copper-clad plate, which comprises epoxy resin and polytetrafluoroethylene. However, it has a low glass transition temperature, and the adhesion between layers and between copper foils is poor, and the dielectric constant is not remarkably exhibited.
Therefore, it is obvious that the development of a high-frequency resin composition with high humidity and heat resistance, high glass transition temperature, high toughness, lower dielectric constant and dielectric loss tangent to meet the requirements of high-performance printed circuit boards such as high-frequency, high-speed and high-density interconnection has positive practical significance.
Disclosure of Invention
The invention aims to provide a high-frequency resin composition, and a prepreg and a laminated board manufactured by using the high-frequency resin composition.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: a high-frequency resin composition comprising, in parts by weight of solids:
(A) fluorine-containing benzoxazine prepolymer: 20-100 parts of a solvent;
(B) epoxy resin: 0-80 parts;
(C) curing agent: 0-30 parts of a solvent;
(D) flame retardant: 0-30 parts of a solvent;
(E) accelerator (b): 0-10 parts;
the structural formula of the fluorine-containing benzoxazine prepolymer is as follows:
wherein R is
R1is-CH2-、-O-、-C(CH3)2-、-SO2-、
n is an integer of 1 to 15.
Above, preferably, the content of the fluorine-containing benzoxazine prepolymer may be 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, or 95 parts by weight. The content of the epoxy resin is 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, or 75 parts by weight.
Preferably, the paint comprises the following components in parts by weight of solid:
(A) fluorine-containing benzoxazine prepolymer: 50-100 parts;
(B) epoxy resin: 10-50 parts;
(C) curing agent: 10-20 parts;
(D) flame retardant: 5-30 parts of a solvent;
(E) accelerator (b): 0.01-10 parts.
In the technical scheme, the fluorine content of the fluorine-containing benzoxazine prepolymer is 5-45%, and the nitrogen content is preferably 3-12%.
When the fluorine content is less than 5%, there is a problem of poor dielectric properties, and when it exceeds 45%, there are problems of adhesion and processability, and when the nitrogen content is within the above-mentioned preferred range, the synergistic flame retardant effect of the fluorine nitrogen element is most excellent.
In the above technical scheme, the epoxy resin is selected from one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, o-cresol novolac epoxy resin, bisphenol a novolac epoxy resin, phenol novolac epoxy resin, trifunctional phenol epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, aralkyl novolac epoxy resin, glycidyl amine epoxy resin, and glycidyl ester epoxy resin. The epoxy resin is 0-80 parts by weight, and can be 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts and 70 parts.
In the above technical scheme, the curing agent is selected from one or more of phenolic resin, linear phenolic resin, dicyandiamide, diaminodiphenyl sulfone, diaminodiphenyl ether, cyanate ester, active ester, polyphenyl ether and acid anhydride.
The above-mentioned phenol NOVOLAC resin is also called novolak resin. The curing agent is 0-30 parts by weight, and can be 5 parts, 10 parts, 20 parts and 25 parts.
The curing agent is preferably cyanate ester, active ester or polyphenyl ether, and when the preferred range is selected, more excellent dielectric property is obtained.
In the technical scheme, the flame retardant is a phosphorus-containing flame retardant or a bromine-containing flame retardant;
the bromine-containing flame retardant is selected from one or more of tribromophenyl maleimide, tetrabromobisphenol A allyl ether, decabromodiphenylethane, brominated polystyrene, brominated polycarbonate, tetrabromobisphenol A and brominated epoxy resin;
the phosphorus-containing flame retardant is selected from one or more of phosphorus-containing epoxy resin, phosphorus-containing phenolic resin, phosphazene compound, phosphate ester compound, phosphorus-containing cyanate ester and phosphorus-containing bismaleimide.
The flame retardant is 5-30 parts by weight, and can be 10 parts, 20 parts, 25 parts, 28 parts and 29 parts.
In the above technical scheme, the accelerator is imidazole, an organic metal salt or a mixture thereof;
wherein the imidazole is 2-methylimidazole, 2-phenylimidazole or 2-ethyl-4-methylimidazole; the organic metal salt is zinc octoate, zinc iso-octoate, stannous octoate, dibutyltin dilaurate, zinc naphthenate, cobalt naphthenate, aluminum acetylacetonate, cobalt acetylacetonate or copper acetylacetonate.
The accelerator is 0.01-10 parts by weight, and can be 0.5 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts and 9 parts.
In the above technical scheme, the resin composition further comprises a filler, and the content of the filler is 20 to 300 parts by weight relative to 100 parts by weight of the total resin composition;
the filler is selected from one or more of crystalline silica, fused silica, spherical silica, alumina, aluminum hydroxide, aluminum nitride, boron nitride, titanium dioxide, strontium titanate, barium sulfate, talcum powder, calcium silicate, calcium carbonate, mica, polytetrafluoroethylene and graphene.
The filler is contained in an amount of 20 to 300 parts by weight, preferably 30 to 150 parts by weight, more preferably 40 to 130 parts by weight, more preferably 50 to 120 parts by weight, more preferably 60 to 100 parts by weight, more preferably 70 to 90 parts by weight, and more preferably 75 to 80 parts by weight, based on 100 parts by weight of the total resin composition.
The inorganic filler can be subjected to surface treatment by a silane coupling agent, and can be directly added or prepared into filler dispersion liquid in advance or prepared into paste to be added into the resin composition; the particle size of the inorganic filler is preferably 0.5 to 10 micrometers.
The invention also discloses a prepreg prepared by the resin composition, the resin composition is dissolved by a solvent to prepare a glue solution, then the reinforcing material is soaked in the glue solution, and the soaked reinforcing material is heated and dried to obtain the prepreg. The preparation method comprises the following steps: dissolving the high-frequency resin composition by using a solvent, uniformly stirring the high-frequency resin composition with the solid content of 60-70 percent, and curing the high-frequency resin composition for 4-8 hours to prepare a resin composition glue solution; then, the reinforcing material is soaked in the resin composition glue solution, and then the soaked reinforcing material is baked for 3-10min at the temperature of 100-200 ℃ and dried to obtain the low-flow prepreg provided by the invention.
The reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric, and is preferably glass fiber cloth. The solvent comprises one or more of N, N-dimethylformamide, acetone, butanone, propylene glycol methyl ether, ethylene glycol ethyl ether, methanol, ethanol, benzene or toluene.
The invention also discloses a laminated board, wherein a metal foil is coated on one side or both sides of one prepreg, or at least 2 prepregs are stacked, then the metal foil is coated on one side or both sides of the prepreg, and hot press forming is carried out, so that the laminated board can be obtained.
The number of prepregs may be determined according to the thickness of the laminate desired, and one or more prepregs may be used. The metal foil may be a copper foil or an aluminum foil, and the thickness thereof is not particularly limited.
The invention also discloses an interlayer insulating film prepared by adopting the resin composition, which is prepared by dissolving the resin composition with a solvent to prepare a glue solution, then coating the glue solution on a carrier film, and heating and drying the carrier film coated with the glue solution.
The heating and drying condition is baking for 1-10 minutes at 50-170 ℃. The solvent comprises one or more of N, N-dimethylformamide, acetone, butanone, propylene glycol methyl ether, ethylene glycol ethyl ether, methanol, ethanol, benzene or toluene. The carrier film may be polyethylene terephthalate (PET) film, release film, copper foil, aluminum foil, etc., and is preferably a PET film. In order to protect the insulating resin layer, the other side of the resin layer is covered with a protective film, which may be the same material as the carrier film.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the fluorine-containing benzoxazine prepolymer is adopted, and the benzoxazine ring structure prepolymer material reduces the concentration of hydroxyl groups generated during curing in the prior art, relatively improves the content of benzene rings, and greatly reduces the dielectric constant and the dielectric loss of products; meanwhile, the fluorine-containing benzoxazine prepolymer has a large number of hydrogen bond acting bodies, so that the problems of difficult forming process, poor adhesion, poor toughness, poor mechanical property and the like caused by less polar groups in the polytetrafluoroethylene technology applied to printed circuit laminates in the prior art are solved, and the adhesion, rigidity and tensile strength of the product are obviously improved; experiments prove that compared with the prior art, the high-temperature-resistant and high-temperature-resistant glass-transition-temperature-resistant glass;
2. the invention adopts the fluorine-containing benzoxazine prepolymer, and the dielectric property of the product is further optimized due to the fluorine-containing element of the prepolymer; meanwhile, the content of fluorine and nitrogen elements is high, so that the intrinsic flame-retardant efficiency is high, the flame-retardant efficiency of the whole system is greatly improved, and the dosage of other flame retardants containing phosphorus or bromine and the like can be greatly reduced;
3. experiments show that the printed circuit laminated board prepared by the composition not only solves the problems of poor cohesiveness, poor mechanical property and the like caused by the defects of the resin of the polytetrafluoroethylene, but also has excellent copper foil peeling strength and high glass transition temperature, and simultaneously has the advantages of stable dielectric constant and low dielectric loss under the high-frequency condition, and can better meet the requirements of high frequency, high speed and high density interconnection;
4. the invention adopts the fluorine-containing benzoxazine prepolymer, and solves the problem of poor compatibility of the polytetrafluoroethylene resin and other resins because the prepolymer or other resins can form a large amount of hydrogen bonds.
Detailed Description
The invention is further described below with reference to the following examples:
examples and comparative examples
A resin composition is prepared by adopting the following components and proportions in the following table 1:
TABLE 1
In the above table:
a1: the fluorine-containing benzoxazine prepolymer has the structural formula
Wherein R is
R1is-CH2-; the fluorine-containing benzoxazine monomer is obtained by ring opening prepolymerization at 80-150 ℃;
a2: the fluorine-containing benzoxazine prepolymer has the structural formula
Wherein R is
R1is-O-; the fluorine-containing benzoxazine monomer is obtained by ring opening prepolymerization at 80-150 ℃;
a3: polytetrafluoroethylene, zhuhixin, inc;
a4: the fluorine-containing benzoxazine monomer has the following structure:
a5: bisphenol a type benzoxazine resin;
b1: DCPD type epoxy resin, manufactured by korea KOLON;
b2: naphthalene ring type epoxy resin, manufactured by Kolon, Korea; (ii) a
C1: cyanate ester, manufactured by Shandong Shengquan;
c2: polyphenylene ether, manufactured by saber;
d: phosphorus-containing flame retardants, tsukamur japan;
e: curing accelerator: zinc octoate;
f: : silicon dioxide with the particle size of 0.5-2 microns is prepared by Jiangsu Murui.
Mixing glue solution:
all components in the formulation were formulated into a thermosetting resin composition glue solution having a solid content of 60% according to the formulation in table 1. The laminate was then made under the following conditions:
reinforcing materials: common electronic grade 2116 glass fiber cloth;
metal foil: 18 micron, electrolytic copper foil;
layer number: 8;
thickness of the formed plate: 1.0 mm;
preimpregnation and semi-solidification conditions: 170 ℃/5 min;
curing conditions are as follows: 150 ℃/60min +220 ℃/150 min;
the test results for each property are shown in table 2:
TABLE 2
The test methods for each property in the table are as follows:
(1) glass transition temperature (Tg): according to differential scanning calorimetry, the measurement was carried out by the DSC method specified by IPC-TM-6502.4.25.
(2) Peel Strength (PS): the peel strength of the metal cap was tested according to the "post thermal stress" experimental conditions in the IPC-TM-6502.4.8 method.
(3) Tin immersion heat resistance: A50X 50mm sample with copper on both sides was immersed in solder at 288 ℃ and the time for delamination of the bubbles was recorded.
(4) Tin immersion heat resistance after moisture treatment: 25 pieces of 100X 100mm substrate samples were held in a pressure cooker at 121 ℃ and 105Kpa for 3hr, and then immersed in a solder bath at 288 ℃ for 2min to observe whether or not delamination and bubbling occurred in the samples.
(5) Dielectric constant: the dielectric constant at 1GHz was measured by the plate method according to IPC-TM-6502.5.5.9.
(6) Dielectric loss tangent: the dielectric dissipation factor at 1GHz was measured by the plate method according to IPC-TM-6502.5.5.9.
(7) Drop hammer impact toughness (brittleness of laminate) Using an impact tester with a drop hammer height of 45cm and a drop hammer weight of 1 kg., the evaluation of good toughness and poor toughness was carried out by using a cross clear which indicates that the toughness of the product is better and is indicated by a character, the cross fuzzy which indicates that the toughness and brittleness of the product are high and is indicated by a character ◎, and the cross clear degree which is between clear and fuzzy indicates that the toughness of the product is general and is indicated by a character ◇.
(8) Coefficient of thermal expansion Z-axis cte (tma): the measurement was carried out according to the IPC-TM-6502.4.24 method.
(9) Flame resistance (flame retardancy): measured according to the UL94 method.
As is clear from the above table, example 1 is superior to comparative example 1 in all of glass transition temperature, peel strength, moist heat resistance, dielectric properties, and toughness; further, from example 2 and example 3 as compared with comparative example 2, and example 5 as compared with comparative example 3, it can be seen that: the laminated board prepared by the invention has good humidity resistance, excellent dielectric property, high glass transition temperature and high toughness, and particularly has excellent reliability in peeling strength and dielectric property.
Compared with the embodiment of the comparative example adopting monomer fluorine-containing benzoxazine, the resin composition has high humidity resistance, high glass transition temperature, lower dielectric constant and dielectric loss tangent value, and can meet the requirements of high-performance printed circuit boards such as high-frequency high-speed and high-density interconnection and the like.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A high-frequency resin composition characterized by comprising, in parts by weight of solids:
(A) fluorine-containing benzoxazine prepolymer: 20-100 parts of a solvent;
(B) epoxy resin: 0-80 parts;
(C) curing agent: 0-30 parts of a solvent;
(D) flame retardant: 0-30 parts of a solvent;
(E) accelerator (b): 0-10 parts;
the structural formula of the fluorine-containing benzoxazine prepolymer is as follows:
2. The resin composition according to claim 1, characterized in that: the paint comprises the following components in parts by weight of solids:
(A) fluorine-containing benzoxazine prepolymer: 50-100 parts;
(B) epoxy resin: 10-50 parts;
(C) curing agent: 10-20 parts;
(D) flame retardant: 5-30 parts of a solvent;
(E) accelerator (b): 0.01-10 parts.
3. The resin composition according to claim 1, characterized in that: the epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, trifunctional phenol type epoxy resin, tetraphenylethane epoxy resin, biphenyl type epoxy resin, naphthalene ring type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl linear novolac epoxy resin, glycidyl amine type epoxy resin and glycidyl ester type epoxy resin.
4. The resin composition according to claim 1, characterized in that: the curing agent is selected from one or more of phenolic resin, dicyandiamide, diaminodiphenyl sulfone, diaminodiphenyl ether, cyanate, active ester, polyphenyl ether and anhydride.
5. The resin composition according to claim 1, characterized in that: the flame retardant is a phosphorus-containing flame retardant or a bromine-containing flame retardant;
the bromine-containing flame retardant is selected from one or more of tribromophenyl maleimide, tetrabromobisphenol A allyl ether, decabromodiphenylethane, brominated polystyrene, brominated polycarbonate, tetrabromobisphenol A and brominated epoxy resin;
the phosphorus-containing flame retardant is selected from one or more of phosphorus-containing epoxy resin, phosphorus-containing phenolic resin, phosphazene compound, phosphate ester compound, phosphorus-containing cyanate ester and phosphorus-containing bismaleimide.
6. The resin composition according to claim 1, characterized in that: the accelerator is imidazole, an organic metal salt or a mixture thereof;
wherein the imidazole is 2-methylimidazole, 2-phenylimidazole or 2-ethyl-4-methylimidazole; the organic metal salt is zinc octoate, zinc iso-octoate, stannous octoate, dibutyltin dilaurate, zinc naphthenate, cobalt naphthenate, aluminum acetylacetonate, cobalt acetylacetonate or copper acetylacetonate.
7. The resin composition according to claim 1, characterized in that: the resin composition further comprises a filler, and the content of the filler is 20-300 parts by weight relative to 100 parts by weight of the total resin composition;
the filler is selected from one or more of crystalline silica, fused silica, spherical silica, alumina, aluminum hydroxide, aluminum nitride, boron nitride, titanium dioxide, strontium titanate, barium sulfate, talcum powder, calcium silicate, calcium carbonate, mica, polytetrafluoroethylene and graphene.
8. A prepreg manufactured by using the resin composition according to any one of claims 1 to 7, wherein: dissolving any one of the resin compositions of claims 1-7 with a solvent to prepare a glue solution, then dipping the reinforcing material in the glue solution, and heating and drying the dipped reinforcing material to obtain the prepreg.
9. A laminate, characterized by: the laminate can be obtained by coating a metal foil on one side or both sides of a prepreg according to claim 8, or by laminating at least 2 prepregs according to claim 8, coating a metal foil on one side or both sides, and hot press forming.
10. An interlayer insulating film produced using the resin composition according to any one of claims 1 to 7, wherein: dissolving the resin composition according to any one of claims 1 to 7 in a solvent to prepare a glue solution, coating the glue solution on a carrier film, and heating and drying the carrier film coated with the glue solution to obtain the interlayer insulating film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810253291.3A CN108485182B (en) | 2018-03-26 | 2018-03-26 | High-frequency resin composition and prepreg and laminated board manufactured by using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810253291.3A CN108485182B (en) | 2018-03-26 | 2018-03-26 | High-frequency resin composition and prepreg and laminated board manufactured by using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108485182A CN108485182A (en) | 2018-09-04 |
| CN108485182B true CN108485182B (en) | 2020-04-28 |
Family
ID=63337866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810253291.3A Active CN108485182B (en) | 2018-03-26 | 2018-03-26 | High-frequency resin composition and prepreg and laminated board manufactured by using same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108485182B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109694553B (en) * | 2018-12-26 | 2021-06-04 | 广东生益科技股份有限公司 | Halogen-free phosphorus-free flame-retardant resin composition, bonding material containing same and metal foil-clad laminate |
| CN109810504A (en) * | 2019-01-24 | 2019-05-28 | 江苏澳盛复合材料科技有限公司 | A kind of bismaleimide resin composition and its solidfied material and composite material |
| JP7384559B2 (en) * | 2019-01-31 | 2023-11-21 | 京セラ株式会社 | High frequency encapsulant resin composition and semiconductor device |
| CN110421928B (en) * | 2019-08-29 | 2021-08-31 | 山东金宝电子股份有限公司 | Preparation method of low-cost and low-loss copper-clad plate for high-speed and high-frequency field |
| CN111154212B (en) * | 2019-09-24 | 2022-10-21 | 张家界皓文树脂合成有限公司 | Thermoplastic high-frequency high-speed resin composition |
| CN112080107A (en) * | 2020-09-27 | 2020-12-15 | 诸暨企为科技有限公司 | Electronic material and preparation process thereof |
| CN113844039A (en) * | 2021-09-27 | 2021-12-28 | 山东金宝电子股份有限公司 | Preparation method of novel low-dielectric-constant copper-clad plate glue solution |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020846A (en) * | 2010-09-29 | 2011-04-20 | 北京化工大学 | Furfurylamine type benzoxazine resin/maleimide compound composition |
| CN106750285A (en) * | 2016-11-23 | 2017-05-31 | 厦门大学 | A kind of fluorine-containing nitrogen benzoxazine polymer-type fire retardant and preparation method thereof |
| CN106832764A (en) * | 2015-12-04 | 2017-06-13 | 广东生益科技股份有限公司 | A kind of halogen-free epoxy resin composition and the prepreg containing it, laminate and printed circuit board |
-
2018
- 2018-03-26 CN CN201810253291.3A patent/CN108485182B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020846A (en) * | 2010-09-29 | 2011-04-20 | 北京化工大学 | Furfurylamine type benzoxazine resin/maleimide compound composition |
| CN106832764A (en) * | 2015-12-04 | 2017-06-13 | 广东生益科技股份有限公司 | A kind of halogen-free epoxy resin composition and the prepreg containing it, laminate and printed circuit board |
| CN106750285A (en) * | 2016-11-23 | 2017-05-31 | 厦门大学 | A kind of fluorine-containing nitrogen benzoxazine polymer-type fire retardant and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis and characterization of fluorinate disomeric polybenzoxazines from core-fluorinated diamine-based benzoxazines;Ya.L.Kobzar et al.;《Polymer》;20180430;第145卷;62-69 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108485182A (en) | 2018-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108485182B (en) | High-frequency resin composition and prepreg and laminated board manufactured by using same | |
| KR101897426B1 (en) | Halogen-free resin composition and prepreg and laminated prepared therefrom | |
| CN108219371B (en) | Epoxy resin composition, prepreg, laminate, and printed wiring board | |
| CN108440901B (en) | High-frequency resin composition, and prepreg, interlayer insulating film and laminated board prepared from high-frequency resin composition | |
| US9528026B2 (en) | Resin composition, resin varnish, prepreg, metal-clad laminate, and printed wiring board | |
| CN109988298B (en) | Modified polyphenyl ether resin, thermosetting resin composition and application thereof | |
| TWI671355B (en) | Resin composition, and pre-preg, metal-clad laminate and printed circuit board prepared using the same | |
| TWI666248B (en) | Maleimide resin composition, prepreg, laminate and printed circuit board | |
| KR20090125810A (en) | Resin composition, prepreg, laminated board, multilayer printed wiring board and semiconductor device | |
| TW201617400A (en) | Thermosetting resin composition and prepreg and laminate prepared therefrom | |
| CN110204862B (en) | Resin composition, prepreg, laminate, metal-clad laminate, and printed wiring board | |
| WO2019127391A1 (en) | Maleimide resin composition, prepreg, laminate and printed circuit board | |
| CN109651763B (en) | Thermosetting resin composition, and prepreg, laminated board and metal foil-clad laminated board using same | |
| US20180312627A1 (en) | Resin Composition, Prepreg, Metal-Clad Laminate, and Printed Circuit Board Using the Same | |
| CN109265654B (en) | Resin composition, and prepreg and laminated board made of same | |
| CN111849122B (en) | Resin composition and application thereof | |
| CN109608828B (en) | Thermosetting resin composition, and prepreg, laminated board and metal foil-clad laminated board using same | |
| CN108219134B (en) | Prepolymer and resin composition of modified composite bismaleimide resin, and prepreg and laminated board manufactured by using prepolymer and resin composition | |
| CN114149659B (en) | Resin composition and use thereof | |
| CN114292492B (en) | Resin composition and application | |
| KR20200055795A (en) | Epoxy resin composition, prepreg, laminated board and printed circuit board | |
| CN113844130A (en) | Preparation method of high-Tg high-frequency copper-clad plate | |
| CN113969041A (en) | Resin composition, prepreg prepared from resin composition and metal foil laminated board | |
| CN114316589B (en) | High-frequency resin composition, prepreg, laminate, interlayer insulating film, high-frequency circuit board, and electronic device | |
| CN111849123B (en) | Epoxy resin composition and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |