CN111635503A - Fluorosilicone modified epoxy resin, preparation method and application thereof - Google Patents

Fluorosilicone modified epoxy resin, preparation method and application thereof Download PDF

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CN111635503A
CN111635503A CN202010605210.9A CN202010605210A CN111635503A CN 111635503 A CN111635503 A CN 111635503A CN 202010605210 A CN202010605210 A CN 202010605210A CN 111635503 A CN111635503 A CN 111635503A
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epoxy resin
modified epoxy
material composition
reaction
resin
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CN111635503B (en
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陈培
黄黎明
周慧
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Hangzhou First Applied Material Co Ltd
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/308—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
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    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention provides a fluorine-silicon modified epoxy resin, a preparation method and application thereof. The fluorine-silicon modified epoxy resin comprises a structure shown in the following formula I:

Description

Fluorosilicone modified epoxy resin, preparation method and application thereof
Technical Field
The invention relates to the technical field of covering film materials, in particular to a fluorine-silicon modified epoxy resin, and a preparation method and application thereof.
Background
In recent years, with the rapid development of electronic technology, the demand for flexible circuit boards has increased and the application fields have also increased. Therefore, higher demands are also made on the performance of the coverlay film for the protective material of the flexible copper foil substrate (FCCL). The cover film is an insulating film coated with an adhesive, and not only resists solder and protects the FPC from moisture, foreign substances and chemicals, but also has the effect of improving the flexibility resistance of the FPC. At present, resin systems of the cover film adhesive are mainly acrylic resin systems and epoxy resin systems. Among them, epoxy resins have excellent adhesion, excellent electrical insulation, good mechanical properties, good corrosion resistance and chemical resistance, and are widely used in various fields such as civil engineering and construction, electronics and electrical, coating plastics, and the like. However, the poor heat resistance, weather resistance and impact damage resistance of epoxy resins have largely limited their wider use.
With the development of the microelectronic industry and the arrival of the 5G era, the circuit integration degree is higher and higher, and a series of problems of increased power consumption, noise interference and the like caused by signal transmission delay and crosstalk and dielectric loss appear. In the large background of the deep development of very large scale integrated circuits, reducing the dielectric constant of interlayer materials becomes an important means for reducing the signal delay time. The dielectric constant (3-4) of epoxy resins has not been able to meet the requirements of the high-speed development of the microelectronics industry. The solution of the problem depends on the development and application of novel low dielectric (less than 3.0) and ultra-low dielectric (less than or equal to 2.2) epoxy resin materials. Because the dipole polarization capability of the C-F bond is smaller and the steric hindrance between molecules can be increased, the introduction of the C-F bond can effectively reduce the dielectric constant, and therefore, the introduction of the F element into the epoxy resin and the formula system thereof proves to be one of effective methods for improving the dielectric loss. At the same time, the C-F bond energy is relatively large (486kJ/mol), CF3The groups are easily enriched on the surface of the resin, so that the resinThe surface tension, the friction factor and the refractive index are low, and the coating has excellent wear resistance, corrosion resistance, pollution resistance, moisture resistance, dielectricity, flame retardance, heat resistance and durability.
CN 1626563A also discloses a preparation method of the fluorine-containing epoxy resin and the derivatives thereof: epoxy resin is prepared by epoxidation of fluorine-containing diphenol compound, dielectric constant and dielectric loss of the resin obtained after curing are obviously reduced, and water absorption is improved, but heat resistance is not mentioned.
CN 109836559A introduces a method for obtaining fluorine-silicon polyurethane prepolymer modified epoxy resin by polymerizing polyurethane prepolymer containing fluorine silicon with conventional epoxy resin, and simultaneously improving the toughness of the epoxy resin; wujiawei et al also use fluorosilicone oil for modifying epoxy resin, and prepares a series of fluorosilicone modified epoxy resins through the reaction between epoxy groups and hydroxyl groups at the end of fluorosilicone oil, so that the high temperature resistance and the hydrophobicity of the epoxy resins are improved. However, the fluorine-containing silicone epoxy resins disclosed in these proposals are also poor in heat resistance and dielectric properties.
For the above reasons, there is a need for a new modified epoxy resin to provide a cover film with good heat resistance and dielectric properties and better overall performance.
Disclosure of Invention
The invention mainly aims to provide a fluorine-silicon modified epoxy resin, a preparation method and application thereof, and aims to solve the problems that in the prior art, an epoxy resin cover film is poor in heat resistance and dielectric property and cannot meet the requirements of high-speed development of the microelectronic industry.
In order to achieve the above object, according to one aspect of the present invention, there is provided a fluorosilicone modified epoxy resin comprising a structure represented by the following formula I:
Figure BDA0002560809240000021
in the formula I, n is an integer of 5 or more.
According to another aspect of the present invention, there is also provided a method for preparing a fluorosilicone modified epoxy resin, comprising the steps of: s1, performing ring-opening bulk polymerization on reaction monomers of trifluoropropylmethylcyclotrisiloxane and/or 2,4,6, 8-tetramethyl-2, 4,6, 8-tetra (3,3, 3-trifluoropropyl) cyclotetrasiloxane under the action of an alkali metal initiator to form a hydroxyl-terminated polyfluorosilicon polymer; s2, carrying out epoxidation reaction on the hydroxyl-terminated polyfluorosilicate polymer and epoxy chloropropane to obtain the fluorosilicone modified epoxy resin.
Further, in step S1, the alkali metal initiator is one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide; preferably, the molar ratio of the alkali metal initiator to the reaction monomer is 0.5-5%, and the reaction temperature of the ring-opening bulk polymerization is 0-40 ℃; preferably, the viscosity of the polymer at the end of the ring-opening bulk polymerization reaction is 2000 to 15000 mPas.
Further, in step S2, the weight ratio of the hydroxyl-terminated polyfluorosilicate polymer to the epichlorohydrin is 1 (4-8); preferably, the epoxidation reaction is carried out under the action of a catalyst, wherein the catalyst is Lewis acid, and the Lewis acid is one or more of anhydrous aluminum chloride, anhydrous tin chloride, anhydrous magnesium chloride and anhydrous zinc chloride; more preferably, the weight of the catalyst is 0.05-0.5% of that of the hydroxyl-terminated poly-fluorine-silicon polymer; preferably, the reaction temperature of the epoxidation reaction is 50-80 ℃, and the reaction time is 3-5 h.
Further, the fluorine-silicon modified epoxy resin comprises epoxy resin, a curing agent, a flame retardant and a toughening agent, wherein 11-45 wt% of the epoxy resin is the fluorine-silicon modified epoxy resin in the claim 1.
Further, the covering film material composition comprises, by weight, 10-25 parts of fluorosilicone modified epoxy resin, 30-50 parts of epoxy resin except for the fluorosilicone modified epoxy resin, 1-3.5 parts of a curing agent, 10-20 parts of a flame retardant and 20-35 parts of a toughening agent.
Further, the covering film material composition also comprises 0.5-3 parts by weight of a curing accelerator; preferably, the curing accelerator is lewis acid or lewis base, and the lewis acid is a metal salt compound, preferably one or more of manganese, iron, cobalt, nickel, copper and zinc salt compounds; the Lewis base is one or more of imidazole, boron trifluoride amine complex, 2-phenylimidazole, 2-ethyl-4-methylimidazole and 4-dimethylaminopyridine.
Further, the epoxy resin except the fluorosilicone modified epoxy resin is a low dielectric epoxy resin with a dielectric constant of 3.5-6.0 and a dielectric loss of 0.005-0.008; preferably, the epoxy resin other than the fluorosilicone-modified epoxy resin is one or more of a dicyclopentadiene type novolac epoxy resin, a biphenyl type epoxy resin, and a naphthalene ring type epoxy resin.
Further, the curing agent is an organic amine curing agent and/or an organic acid anhydride curing agent; preferably, the organic amine curing agent is one or more of 4,4 '-diaminodiphenyl ether, 4' -diaminodiphenylmethane, 4 '-diaminodiphenylsulfone, 4' -bis (2,2 '-bistrifluoromethyl-4-aminophenoxy) benzene, 3', 5,5 '-tetramethyl-4, 4' -diaminodiphenylmethane; preferably, the organic acid anhydride curing agent is one or more of 4-methyl hexahydrophthalic anhydride, 4-methyl tetracyanophthalic anhydride, tetrahydrophthalic anhydride and hexahydrophthalic anhydride; preferably, the flame retardant is a metal hydroxide and/or a phosphorus-containing compound, preferably the metal hydroxide is magnesium hydroxide and/or aluminum hydroxide, preferably the phosphorus-containing compound is one or more of trichloroethyl phosphate, triethyl phosphate, tricresyl phosphate, dimethyl methylphosphonate, bisphenol a-bis (diphenyl phosphate), tert-butylated triphenyl phosphate, diethyl ethylphosphate and dialkyl phosphate; preferably, the toughening agent is one or more of polyurethane resin, nitrile rubber aniline resin, polyimide resin, styrene-butadiene rubber and styrene-butadiene-styrene block copolymer, preferably the polyurethane resin is polyaminomethyl ester resin, preferably the nitrile rubber is carboxyl-terminated nitrile rubber and/or epoxy-terminated nitrile rubber.
Further, the covering film material composition also comprises a solvent, wherein the solvent is preferably one or more of butanone, acetone, toluene, xylene, dimethyl formamide and propylene glycol methyl ether; preferably, the solid content of the covering film material composition is 30-70 wt%.
The fluorosilicone modified epoxy resin provided by the invention has low dielectric constant, dielectric loss and excellent heat resistance. The fluorine-silicon modified epoxy resin is applied to an epoxy resin series covering film, can obviously improve the heat resistance of the covering film, has low dielectric property, meets the high-frequency and high-efficiency transmission requirement of signals in the 5G era, and can be used as a flexible copper-clad plate and a halogen-free covering film material in the fields of intelligent products (glasses, earphones, mobile phones, watches and the like), cameras, video cameras, portable flat panel displays, military space vehicles and the like.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background section, prior art epoxy-based coverlay films have poor heat resistance and dielectric properties and cannot meet the requirements of the rapidly developing microelectronics industry.
In order to solve the above problems, the present invention provides a fluorosilicone modified epoxy resin, which has a structure represented by formula I:
Figure BDA0002560809240000031
in the formula I, n is an integer of 5 or more.
The fluorosilicone modified epoxy resin provided by the invention has low dielectric constant, dielectric loss and excellent heat resistance. The fluorine-silicon modified epoxy resin is applied to an epoxy resin series covering film, can obviously improve the heat resistance of the covering film, has low dielectric property, meets the high-frequency and high-efficiency transmission requirement of signals in the 5G era, and can be used as a flexible copper-clad plate and a halogen-free covering film material in the fields of intelligent products (glasses, earphones, mobile phones, watches and the like), cameras, video cameras, portable flat panel displays, military space vehicles and the like.
In addition to the above beneficial effects, the fluorosilicone modified epoxy resin provided by the present invention has good compatibility with other components in the epoxy resin-based coverlay composition, and the formed coverlay composition has good coatability, adhesiveness, and the like.
According to another aspect of the present invention, there is also provided a method for preparing the above fluorosilicone modified epoxy resin, comprising the steps of: s1, reacting the monomer trifluoropropylmethylcyclotrisiloxane (D)3F) And/or 2,4,6, 8-tetramethyl-2, 4,6, 8-tetrakis (3,3, 3-trifluoropropyl) cyclotetrasiloxane (D)4F) Carrying out ring-opening bulk polymerization under the action of an alkali metal initiator to form a hydroxyl-terminated polyfluorosilicate polymer; s2, carrying out epoxidation reaction on the hydroxyl-terminated polyfluorosilicate polymer and epoxy chloropropane to obtain the fluorosilicone modified epoxy resin. The modified epoxy resin can be obtained by the method through ring-opening bulk polymerization and terminal hydroxyl epoxidation reaction in sequence. The method is convenient to operate, simple in process, mild in reaction condition, high in reaction conversion rate and the like, and is very suitable for large-scale application.
In order to improve the reaction efficiency, in a preferred embodiment, the alkali metal initiator is one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide; more preferably, the molar ratio of the alkali metal initiator to the reaction monomer is 0.5-5%, and the reaction temperature of the ring-opening bulk polymerization is 0-40 ℃; preferably, the viscosity of the polymer at the end of the ring-opening bulk polymerization reaction is 2000 to 15000 mPas. In the actual operation process, the whole reaction process is preferably carried out under the protection of nitrogen, and the reaction time is about 30 min. And (3) after the reaction is finished, preferably adding hydrochloric acid to terminate the reaction, wherein the use amount of the hydrochloric acid is 3-5 times of the mole number of the initiator, extracting after the termination, and washing to obtain the hydroxyl-terminated polyfluorosilicate polymer.
In a preferred embodiment, in the step S2, the weight ratio of the hydroxyl-terminated polyfluorosilicate polymer to the epichlorohydrin is 1 (4-8); this can further improve the epoxidation efficiency of the hydroxy-terminated fluorosilicone polymer. Preferably, the epoxidation reaction is carried out under the action of a catalyst, wherein the catalyst is Lewis acid, and the Lewis acid is one or more of anhydrous aluminum chloride, anhydrous tin chloride, anhydrous magnesium chloride and anhydrous zinc chloride (the catalysis effect is optimal by adopting the anhydrous tin chloride); more preferably, the weight of the catalyst is 0.05-0.5% of that of the hydroxyl-terminated poly-fluorine-silicon polymer; preferably, the reaction temperature of the epoxidation reaction is 50-80 ℃, and the reaction time is 3-5 h. In the actual operation process, after the epoxidation reaction is finished, the reaction solution is preferably extracted and washed to obtain the final target product.
According to another aspect of the invention, the covering film material composition comprises epoxy resin, a curing agent, a flame retardant and a toughening agent, wherein 11-45 wt% of the epoxy resin is the fluorine-silicon modified epoxy resin. The modified epoxy resin with good dielectric property and heat resistance is adopted, and the modified epoxy resin has good compatibility with other compositions, so that the covering film formed by coating and curing the covering film material composition provided by the invention has good heat resistance and low dielectric property, low dielectric constant and low dielectric loss, meets the high-frequency and high-efficiency transmission requirements of signals in the 5G era, and can be used as a flexible copper-clad plate and halogen-free covering film material in the fields of intelligent products (glasses, earphones, mobile phones, watches, and the like), cameras, video cameras, portable flat panel displays, military space vehicles and the like.
In a preferred embodiment, the covering film material composition comprises, by weight, 10 to 25 parts of a fluorosilicone modified epoxy resin, 30 to 50 parts of an epoxy resin other than the fluorosilicone modified epoxy resin, 1 to 3.5 parts of a curing agent, 10 to 20 parts of a flame retardant, and 20 to 35 parts of a toughening agent. The dosage relation of each component is controlled within the range, and the finally formed covering film has better comprehensive performance.
In order to further promote the curing efficiency of the composition, in a preferred embodiment, the covering film material composition further comprises 0.5-3 parts by weight of a curing accelerator; preferably, the curing accelerator is lewis acid or lewis base, the lewis acid is metal salt compound, preferably one or more of manganese, iron, cobalt, nickel, copper, zinc salt compound, such as organic carboxylate, such as zinc octoate, cobalt zincate, etc.; the Lewis base is one or more of imidazole (imidazole), boron trifluoride amine complex (2-methylimidazole,2MI), 2-phenylimidazole (2-phenyl-1H-imidizole, 2PZ), 2-ethyl-4-methylimidazole (2-ethyl-4-methylimidazole,2E4MI), 4-dimethylaminopyridine (4-dimethylaminopyridine, DMAP).
In a preferred embodiment, the epoxy resin other than the fluorosilicone-modified epoxy resin is a low dielectric epoxy resin having a dielectric constant of 3.5 to 5.5 and a dielectric loss of 0.005 to 0.007; preferably, the epoxy resin other than the fluorosilicone-modified epoxy resin is one or more of a dicyclopentadiene type novolac epoxy resin (e.g., HP-7200, Japan DIC; SEV-3408, Shandong industries), a biphenyl type epoxy resin (e.g., YX4000, Mitsubishi chemical, SN495V2, Nippon Nissin iron) and a naphthalene type epoxy resin (e.g., NC-7000L, Nippon Chemicals; HP-6000, Japan DIC). On the one hand, the accumulated epoxy resin has better comprehensive performance, and on the other hand, the combined use of the accumulated epoxy resin and the epoxy resin contributes to further improving the low dielectric property and the heat resistance of the covering film.
The curing agent may be of a type commonly used in the art, and of course, in order to enhance the curing effect, the flame retardant effect and the toughening effect, in a preferred embodiment, the curing agent is an organic amine curing agent and/or an organic acid anhydride curing agent; preferably, the organic amine curing agent is one or more of 4,4 ' -diaminodiphenyl ether (ODA), 4 ' -diaminodiphenylmethane (DDM), 4 ' -diaminodiphenyl sulfone (4,4 ' -DDS), 4 ' -bis (2,2 ' -bistrifluoromethyl-4-aminophenoxy) benzene (6FAPB), 3 ', 5,5 ' -tetramethyl-4, 4 ' -diaminodiphenylmethane (TMDA); preferably, the organic acid anhydride curing agent is one or more of 4-methyl hexahydrophthalic anhydride (HMPA), 4-methyl tetracyanophthalic anhydride (MeTHPA), tetrahydrophthalic anhydride (THPA) and hexahydrophthalic anhydride (HHPA); preferably, the flame retardant is a metal hydroxide and/or a phosphorus-containing compound, preferably, the metal hydroxide is magnesium hydroxide and/or aluminum hydroxide (the particle size is preferably 1-5 μm), and preferably, the phosphorus-containing compound is one or more of trichloroethyl phosphate, triethyl phosphate, tricresyl phosphate, dimethyl methylphosphonate, bisphenol A-bis (diphenyl phosphate), tert-butylated triphenyl phosphate, diethyl ethylphosphate and dialkyl phosphate; preferably, the toughening agent is one or more of polyurethane resin, nitrile rubber aniline resin, polyimide resin, styrene-butadiene rubber and styrene-butadiene-styrene block copolymer, preferably the polyurethane resin is polyaminomethyl ester resin, preferably the nitrile rubber is carboxyl-terminated nitrile rubber and/or epoxy-terminated nitrile rubber.
The composition may further include a solvent to dissolve only the epoxy resin and the fluorosilicone resin and disperse the curing agent, the curing accelerator, the flame retardant, and the toughening agent, preferably without reacting with them. In a preferred embodiment, the coverlay material composition further comprises a solvent, preferably one or more of butanone, acetone, toluene, xylene, dimethylformamide, propylene glycol methyl ether; preferably, the solid content of the covering film material composition is 30-70 wt%.
The preparation method of the composition is simple, and for example, the composition can be prepared by the following steps: firstly, adding a curing agent, a curing accelerator, a flame retardant and a solvent into a high-speed stirring reactor for mixing, wherein the stirring speed is more than 2000rpm, and the stirring time is 30 min. And then adding the fluorosilicone modified epoxy resin, other epoxy resins and the flame retardant into the reactor, mixing and stirring at room temperature for 30 min. And finally, adding a toughening agent into the reactor, and mixing for 30min to prepare the fluorosilicone modified epoxy resin composition. Wherein, the viscosity of the finally obtained resin composition is preferably controlled to be 800-2000 mPas and is optimally controlled to be 800-1200 mPas at 25 ℃.
In a specific use process, after the resin composition is subjected to a coating step, a baking step and a curing step, a cover film is formed on the surface of the base material. Optionally, a release paper may be provided on the other side of the cover film (the side not in contact with the substrate) to facilitate transportation and storage of the produced cover film. Specifically, the above-mentioned production method is to coat the above-mentioned composition on the surface of a substrate, and the above-mentioned substrate may be a Polyimide (PI) plastic film substrate (thickness is 12.5 μm). And (3) carrying out a baking step on the coated substrate to remove the solvent in the resin composition. Then, the temperature was adjusted to 80 ℃ and 1.6Kgf/cm2Press-fitting to obtain the packaged product.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Examples
Preparing fluorine-silicon modified epoxy resin:
step 1, hydroxyl-terminated fluorosilicone polymer anion ring-opening bulk polymerization: the polymerized monomer is trifluoropropylmethyl cyclotrisiloxane (D)3F) The initiator is potassium hydroxide initiator; adding D into the reactor3F and potassium hydroxide, controlling the initiator (molar ratio) to be 1.0%, controlling the reaction temperature to be 20 ℃, controlling the reaction time to be 30min, and carrying out the whole reaction process under the protection of nitrogen; finally, the addition of hydrochloric acid was terminated, and the amount of the hydrochloric acid was 5 times (molar ratio) as much as that of the initiator. After the reaction was completed, extraction was performed with ethyl acetate, and washing was performed. Obtaining the hydroxyl-terminated polyfluorosilicate polymer. The resultant polymer had a viscosity of about 6000 mPas, corresponding to n of formula I of about 20.
Step 2 epoxidation of hydroxyl-terminated groups: and adding 500 parts by mass of epoxy chloropropane to 100 parts by weight of the synthesized hydroxyl-terminated fluorosilicone polymer to react for 3 hours at a constant temperature (50 ℃) under the action of a catalyst, extracting by using ethyl acetate, and washing to obtain the final fluorine-silicon modified epoxy resin, wherein the catalyst is anhydrous tin chloride (1.5%).
Preparation of epoxy resin coating material composition:
adding the curing agent, the curing accelerator, the flame retardant and the solvent into a high-speed stirring reactor for mixing, wherein the stirring speed is more than 2000rpm, and the stirring time is 30 min. And then adding the fluorosilicone modified epoxy resin, other epoxy resins and the flame retardant into the reactor, mixing and stirring at room temperature for 30 min. And finally, adding a toughening agent into the reactor, and mixing for 30min to prepare the fluorosilicone modified epoxy resin composition.
The composition formulations in the examples are given in table 1 below:
TABLE 1
Figure BDA0002560809240000071
HP-7200 Dicyclopentadiene Novolac epoxy resin, Nippon DIC Ltd
SEV-3408 dicyclopentadiene novolac epoxy resin, Shengdong industry
PIAD: soluble polyimide, crude chemical
P-260 soluble polyimide, space chemistry
BX-39SS polyurethane, Toyo Boseki
Hycar-1042 Acrylonitrile-butadiene rubber, south emperor chemical
OP-935 aluminium Diethylphosphate, Crainen chemical Co
H-42M aluminum hydroxide, Showa chemical industry
And (3) removing the release paper 130 from the fluorine-silicon modified epoxy resin covering film packaging product, and curing for 150h and 3h to obtain the composite dielectric layer.
Evaluation of main properties:
1. measurement of dielectric constant (Dk) and dielectric loss (Df)
The resin composition composite dielectric layers obtained in the examples were dried at 150 ℃ for 30min, and the dielectric constant and dielectric loss of each composite dielectric layer were measured by the split dielectric resonator (SPDR) method using a resonator (agilent E5071 bean) at 25 ℃ and 50% RH.
2. Thermogravimetric TGA test
TGA test was conducted using 10mg of the resin composition composite dielectric layer obtained in the examples, and the test procedure was 20 DEG/min, and room temperature was raised to 600 ℃ to obtain an initial decomposition temperature.
3. Tensile strength
The resin composition composite dielectric layer obtained in the examples was cut into a test piece having a size of 152.4 cm × 12.7 cm. Next, the tensile strength of these test pieces was measured by using an universal tensile machine at a tensile rate of 50.8 m/h.
4. Flame resistance
The flame resistance referred to herein in the present invention is defined in UL-94V 0. Specifically, the composite dielectric layer was subjected to 2 burning tests for 10 seconds each, and flame resistance was excellent if the flame was extinguished within 30 seconds and no combustible substance dropped. On the contrary, the flame resistance is not good, and the specific evaluation criteria are as follows:
o: the flame is extinguished within 30 seconds, no combustible substance falls, and the flame resistance is good
X: the flame is not extinguished within 30 seconds, or the burning substances fall off, and the flame resistance is poor
The characterization results are shown in table 2 below:
TABLE 2
Figure BDA0002560809240000081
Figure BDA0002560809240000082
As a result of the experiment, it was found that the coverlay films of examples 1 to 8 all had low dielectric constant (Dk < 3.0) and low dielectric loss (Df. ltoreq.0.0080) while maintaining good strength, heat resistance and flame retardancy. From examples 1 to 5, it can be seen that the dielectric constant/dielectric loss value loss is reduced and the performance is better as the addition amount of the fluorosilicone modified epoxy resin is increased within a certain range. As can be seen from comparative example 1, the composition without the fluorosilicone modified epoxy resin had a high dielectric constant of 3.12, a thermal decomposition temperature of 248 ℃ and poor heat resistance.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A fluorine-silicon modified epoxy resin is characterized by comprising a structure shown in the following formula I:
Figure FDA0002560809230000011
in the formula I, n is an integer of more than 5.
2. The preparation method of the fluorosilicone modified epoxy resin of claim 1, comprising the steps of:
s1, performing ring-opening bulk polymerization on reaction monomers of trifluoropropylmethylcyclotrisiloxane and/or 2,4,6, 8-tetramethyl-2, 4,6, 8-tetra (3,3, 3-trifluoropropyl) cyclotetrasiloxane under the action of an alkali metal initiator to form a hydroxyl-terminated polyfluorosilicon polymer;
s2, carrying out epoxidation reaction on the hydroxyl-terminated polyfluorosilicate polymer and epoxy chloropropane to obtain the fluorosilicone modified epoxy resin.
3. The preparation method according to claim 2, wherein in the step S1, the alkali metal initiator is one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide;
preferably, the molar ratio of the alkali metal initiator to the reaction monomer is 0.5-5%, and the reaction temperature of the ring-opening bulk polymerization is 0-40 ℃;
preferably, the viscosity of the polymer at the end of the ring-opening bulk polymerization reaction is 2000 to 15000 mPas.
4. The method according to claim 2 or 3, wherein in step S2, the weight ratio of the hydroxyl-terminated polyfluorosilicate polymer to the epichlorohydrin is 1 (4-8);
preferably, the epoxidation reaction is carried out under the action of a catalyst, wherein the catalyst is a Lewis acid, and the Lewis acid is one or more of anhydrous aluminum chloride, anhydrous tin chloride, anhydrous magnesium chloride and anhydrous zinc chloride; more preferably, the weight of the catalyst is 0.05-0.5% of that of the hydroxyl-terminated poly-fluorine-silicon polymer;
preferably, the reaction temperature of the epoxidation reaction is 50-80 ℃, and the reaction time is 3-5 h.
5. The covering film material composition is characterized by comprising epoxy resin, a curing agent, a flame retardant and a toughening agent, wherein 11-45 wt% of the epoxy resin is the fluorosilicone modified epoxy resin in claim 1.
6. The coverlay material composition of claim 5, wherein the coverlay material composition comprises, by weight, 10 to 25 parts of the fluorosilicone modified epoxy resin, 30 to 50 parts of an epoxy resin other than the fluorosilicone modified epoxy resin, 1 to 3.5 parts of the curing agent, 10 to 20 parts of the flame retardant, and 20 to 35 parts of the toughening agent.
7. The coverlay material composition of claim 6, further comprising 0.5 to 3 parts by weight of a curing accelerator;
preferably, the curing accelerator is a lewis acid or a lewis base, and the lewis acid is a metal salt compound, preferably one or more of manganese, iron, cobalt, nickel, copper and zinc salt compounds; the Lewis base is one or more of imidazole, boron trifluoride amine complex, 2-phenylimidazole, 2-ethyl-4-methylimidazole and 4-dimethylaminopyridine.
8. The coverlay material composition of any one of claims 5-7, wherein the epoxy resin other than the fluorosilicone modified epoxy resin is a low dielectric epoxy resin having a dielectric constant of 3.5-6.0 and a dielectric loss of 0.005-0.008;
preferably, the epoxy resin other than the fluorosilicone modified epoxy resin is one or more of a dicyclopentadiene type novolac epoxy resin, a biphenyl type epoxy resin, and a naphthalene ring type epoxy resin.
9. The mulch film material composition according to any one of claims 5 to 7 wherein the curing agent is an organic amine curing agent and/or an organic anhydride curing agent; preferably, the organic amine curing agent is one or more of 4,4 '-diaminodiphenyl ether, 4' -diaminodiphenylmethane, 4 '-diaminodiphenylsulfone, 4' -bis (2,2 '-bistrifluoromethyl-4-aminophenoxy) benzene, 3', 5,5 '-tetramethyl-4, 4' -diaminodiphenylmethane; preferably, the organic acid anhydride curing agent is one or more of 4-methyl hexahydrophthalic anhydride, 4-methyl tetracyanophthalic anhydride, tetrahydrophthalic anhydride and hexahydrophthalic anhydride;
preferably, the flame retardant is a metal hydroxide and/or a phosphorus-containing compound, preferably the metal hydroxide is magnesium hydroxide and/or aluminum hydroxide, preferably the phosphorus-containing compound is one or more of trichloroethyl phosphate, triethyl phosphate, tricresyl phosphate, dimethyl methylphosphonate, bisphenol a-bis (diphenyl phosphate), tert-butylated triphenyl phosphate, diethyl ethylphosphate and dialkyl phosphate;
preferably, the toughening agent is one or more of polyurethane resin, nitrile rubber aniline resin, polyimide resin, styrene-butadiene rubber and styrene-butadiene-styrene block copolymer, the polyurethane resin is preferably polyaminomethyl ester resin, and the nitrile rubber is preferably carboxyl-terminated nitrile rubber and/or epoxy-terminated nitrile rubber.
10. The mulch film material composition of claims 5-7 wherein the mulch film material composition further comprises a solvent, preferably one or more of butanone, acetone, toluene, xylene, dimethylformamide, propylene glycol methyl ether; preferably, the solid content of the covering film material composition is 30-70 wt%.
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