CN117264419B - Halogen-free flame-retardant high-Tg resin composition, resin glue solution, prepreg, copper-clad plate and preparation method thereof, and circuit board - Google Patents

Halogen-free flame-retardant high-Tg resin composition, resin glue solution, prepreg, copper-clad plate and preparation method thereof, and circuit board Download PDF

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Publication number
CN117264419B
CN117264419B CN202311568832.9A CN202311568832A CN117264419B CN 117264419 B CN117264419 B CN 117264419B CN 202311568832 A CN202311568832 A CN 202311568832A CN 117264419 B CN117264419 B CN 117264419B
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resin
resin composition
prepreg
copper
benzoxazine
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CN117264419A (en
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岳杰
孙玉杰
张锋
张帝
邢云亮
顾维科
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CHENGDU KEYI POLYMER TECHNOLOGY CO LTD
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CHENGDU KEYI POLYMER TECHNOLOGY CO LTD
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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
    • 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
    • B32B5/22—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of 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 C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08L79/085—Unsaturated polyimide precursors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • 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
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • 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
    • 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
    • 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
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/308—Heat stability
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • 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
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • 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
    • C08J2379/00—Characterised by the use of 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 C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08J2479/00—Characterised by the use of 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 C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention provides a halogen-free flame-retardant high Tg resin composition, a resin glue solution, a prepreg, a copper-clad plate, a preparation method thereof and a circuit board, and relates to the field of materials; the benzoxazine resin is a benzoxazine resin containing nitrile groups and the nitrile groups are end groups. The mass ratio of the bismaleimide resin to the benzoxazine resin to the epoxy resin is 60 (10-50): 10-40. The invention also provides a resin glue solution, a prepreg and a copper-clad plate prepared from the resin composition. The halogen-free flame-retardant high Tg resin composition has the properties of high Tg, low CTE, good dielectric property and the like, and the glass transition temperature of a copper-clad plate prepared by the halogen-free flame-retardant high Tg resin composition is not lower than 290 ℃, the dielectric constant is not higher than 4, the dielectric loss is not higher than 0.007, and the X/Y axis thermal expansion coefficient at the temperature of 30-300 ℃ is not higher than 7 ppm/DEGC.

Description

Halogen-free flame-retardant high-Tg resin composition, resin glue solution, prepreg, copper-clad plate and preparation method thereof, and circuit board
Technical Field
The invention relates to the technical field of materials, in particular to a halogen-free flame-retardant high Tg resin composition, a resin glue solution, a prepreg, a copper-clad plate, a preparation method of the copper-clad plate and a circuit board.
Background
With the rapid development of electronic industrialization, electronic products are increasingly miniaturized, thinned and multifunctional, so that semiconductor manufacturing is continuously advanced. Further, the printed circuit board (Printed Circuit Board, PCB) is required to have the characteristics of light weight, high integration and high reliability, and simultaneously, higher requirements are put on the aspects of environmental protection, heat resistance, flame retardance and the like of the PCB. Among them, a substrate-like PCB (SLP) is widely used in smart phones, notebook computers, tablet computers, automotive electronics and other electronic terminal products, which is a popular choice for next-generation PCB hard boards. The minimum line width/spacing of the SLP type carrier plate is as follows: 20-30 μm, and a plate thickness of 0.2-1.5 mm. The technical parameter nodes are arranged between the IC carrier plate and the HDI high-density interconnection plate, and can replace the traditional HDI PCB, although the grade of the IC carrier plate cannot be achieved. However, under the same area, the bearing number of the electronic components of the SLP board can be twice as high as that of the HDI high-density interconnection board. However, SLP type carrier plates require that the resin materials used are environment-friendly halogen-free systems, and because of high use temperature, the glass transition temperature (Tg) and dimensional stability of the materials are required to be high, and meanwhile, low dielectric constants are required to meet the trend of future light and thin, but the resin materials in the prior art are difficult to simultaneously meet the requirements of the glass transition temperature, the dimensional stability, the dielectric constants and the halogen-free.
Disclosure of Invention
The invention aims to provide a halogen-free flame-retardant high Tg resin composition, a resin glue solution, a prepreg, a copper-clad plate, a preparation method thereof and a circuit board; the resin composition can give consideration to the performances of glass transition temperature, dimensional stability, dielectric constant and the like on the premise of no halogen, so that the copper-clad plate and the circuit board based on the resin composition can meet the performance requirements of environmental protection, heat resistance, flame retardance, dielectric constant and the like.
In a first aspect, embodiments of the present invention provide a halogen-free flame retardant high Tg resin composition comprising a resin, a curing agent, a filler, and a solvent, the resin comprising a bismaleimide resin, a benzoxazine resin, and an epoxy resin;
wherein the benzoxazine resin is benzoxazine resin containing nitrile groups and the nitrile groups are end groups;
the bismaleimide resin is any one or a combination of at least two of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3, 5-diethyl-4-maleimidophenyl) methane, bis (3, 5-dimethyl-4-maleimidophenyl) methane or 2,2' -bis [4- (4-maleimidophenoxy) phenyl ] propane.
The mass ratio of the bismaleimide resin to the benzoxazine resin to the epoxy resin is 60 (10-50): 10-40.
Further, in some embodiments of the present application, the mass ratio of the bismaleimide resin, the benzoxazine resin and the epoxy resin is 60 (20-35): 20-30.
Further, in some embodiments of the present application, the benzoxazine resin is any one or a combination of at least two of a dicyclopentadiene type benzoxazine resin containing nitrile groups and a benzoxazine resin containing nitrile groups.
Further, in some embodiments of the present application, the benzoxazine resin is a dicyclopentadiene type benzoxazine resin containing nitrile groups.
Further, in some embodiments of the present application, the benzoxazine resin is a dicyclopentadiene type benzoxazine resin containing nitrile groups with a weight average molecular weight of 1000-10000, and the benzoxazine resin has a molecular weight distribution coefficient of 1.0-4.0, and a softening point of 100-160 ℃.
Further, in some embodiments of the present application, the benzoxazine resin is selected from one or a combination of at least two of the compounds of the formula:
a formula I;
a formula II;
wherein n in the formula I is an integer of 0 to 10.
Further, in some embodiments of the present application, the epoxy resin is a halogen-free and phosphorus-free epoxy resin selected from any one or a mixture of at least two of a phenolic epoxy resin, a biphenyl epoxy resin, a naphthol epoxy resin, a dicyclopentadiene epoxy resin, or a multifunctional epoxy resin.
Further, in some embodiments of the present application, the curing agent is selected from any one or a mixture of two of an anhydride-based curing agent or an amine-based curing agent.
Further, in some embodiments of the present application, the filler is any one or a mixture of at least two of barium sulfate, talc, crystalline silica, fused silica, amorphous silica, spherical silica, nano silica, magnesium carbonate, calcium carbonate, nano calcium carbonate, alumina, aluminum hydroxide, or silica micropowder.
Further, in some embodiments of the present application, the solvent is any one or a mixture of at least two of ketones, esters, ethers, alcohols, or the like.
Further, in some embodiments of the present application, the resin composition includes, in parts by mass:
100 parts of resin
1-5 parts of curing agent
50-200 parts of filler
50-300 parts of solvent.
In a second aspect, the present application also provides a resin glue solution, which is prepared from the halogen-free flame-retardant high Tg resin composition according to the first aspect.
Further, in some embodiments of the present application, the solid content of the resin glue solution is 50% -70%.
In a third aspect, the present application also provides a prepreg comprising a reinforcing material and an attachment attached to the reinforcing material; the attachment is obtained by curing the resin composition according to the first aspect or the resin dope according to the second aspect.
Further, in some embodiments of the present application, the reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics.
In a fourth aspect, the present application also provides a method for preparing a prepreg, comprising the steps of:
providing a reinforcing material, the resin composition of the first aspect or the resin dope of the second aspect;
and enabling the resin composition or the resin glue solution to be attached to the surface of the reinforcing material and semi-curing the resin composition or the resin glue solution to obtain the prepreg.
Further, in some embodiments of the present application, adhering a resin composition or a resin cement to the surface of the reinforcing material and semi-curing the resin composition or the resin cement includes:
impregnating the reinforcing material with the resin composition for 0.5-1min;
heat treating the reinforcing material with the resin composition or resin glue solution at 100-200deg.C for 1-10min.
In a fifth aspect, the present application further provides an electrical copper-clad plate, which includes the prepreg of the third aspect or the prepreg prepared by the preparation method of the prepreg of the fourth aspect.
Further, in some embodiments of the present application, the electrical copper-clad plate further comprises a copper foil; copper foil is coated on one side or both sides of the prepreg.
Further, in some embodiments of the present application, the glass transition temperature of the electric copper-clad plate is not lower than 290 ℃, the dielectric constant is not higher than 4, the dielectric loss is not higher than 0.007, and the X/Y axis thermal expansion coefficient at a temperature of 30-300 ℃ is not higher than 7 ppm/°c.
In a sixth aspect, the present application further provides a circuit board, where the circuit board includes the electrical copper-clad plate according to the fifth aspect.
The embodiment of the application provides a halogen-free flame-retardant high Tg resin composition, a resin glue solution, a prepreg, a copper-clad plate, a preparation method thereof and a circuit board, wherein the resin composition adopts a bismaleimide/nitrile-containing benzoxazine/epoxy resin composition object ternary mixing system, and a polymer obtained by curing the resin composition can have good flame-retardant and temperature-resistant effects without adding halogen-containing resin; meanwhile, the epoxy resin and the DCPD-type benzoxazine resin containing nitrile groups are synergistic, so that the crosslinking density of the polymer obtained by curing can be better improved, and the temperature resistance and the glass transition temperature of the polymer obtained by curing are improved; and simultaneously, bismaleimide resin is added, so that the temperature resistance and the glass transition temperature of the polymer obtained by curing are optimized, and meanwhile, the dimensional stability of the polymer obtained by curing is better, and simultaneously, the polymer has lower dielectric constant and lower dielectric loss. In addition, the resin composition provided by the application also overcomes the defects of higher curing temperature and longer curing time of the bismaleimide, so that the curing reaction temperature and the curing time are more beneficial to production and processing; meanwhile, the defect of brittleness of the benzoxazine resin is overcome, so that the cured polymer has high strength, good toughness and better processability, and simultaneously has good flame retardance, temperature resistance, dimensional stability and lower dielectric property, and meets the performance requirements of the SLP carrier board such as glass transition temperature, thermal stability, flame retardance and dielectric property under the environment-friendly condition. Meanwhile, the resin composition can enable copper-clad plates and circuit boards based on the resin composition to have the advantages of high glass transition temperature, excellent heat resistance, halogen-free flame retardance, low dielectric constant and good process processability, and the resin composition has excellent comprehensive performance and can be better applied to the field of carrier-like plates. The glass transition temperature of the polymer, the copper-clad plate and the circuit board obtained based on the curing of the resin composition can reach more than 300 ℃, the minimum dielectric constant (10 GHz) can reach 3.73, the minimum dielectric constant (10 GHz) can reach 0.005, the thermal expansion coefficient of an X/Y axis at the temperature of 30-300 ℃ is not higher than 7 ppm/DEGC, and the flame retardant property can reach V-0 level.
Description of the embodiments
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below in conjunction with specific examples of the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
[ resin ]
The composition is a ternary mixed system of three resin monomers including bismaleimide resin, benzoxazine resin and epoxy resin, and the mass ratio of the bismaleimide resin, the benzoxazine resin and the epoxy resin in the whole composition is not more than 40%, so that the solid content in a resin glue solution formed based on the resin composition is not more than 40%, and the resin glue solution is easy to glue. In addition, in the application, the mass ratio of the bismaleimide resin, the benzoxazine resin and the epoxy resin to the three resin monomers needs to be controlled within the range of 60 (10-50): 10-40, so that the comprehensive performance of the resin is better. Further, the mass ratio of the bismaleimide resin to the benzoxazine resin to the epoxy resin is 60 (20-35): 20-30.
Bismaleimide resin
The bismaleimide resin is another resin system derived from a polyimide resin system, is a difunctional compound taking Maleimide (MI) as an active end group, has fluidity and moldability similar to those of epoxy resin, but because the bismaleimide resin contains benzene rings, imide heterocycle and has higher crosslinking density, the cured product of the bismaleimide resin has excellent heat resistance, the Tg of the bismaleimide resin is generally higher than 250 ℃, the crosslinking density of a polymer formed by curing the composition provided by the application can be improved, and further the heat resistance of the polymer formed by curing the resin composition is improved. And since the bismaleimide resin used in the present application is any one or a combination of at least two of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3, 5-diethyl-4-maleimidophenyl) methane, bis (3, 5-dimethyl-4-maleimidophenyl) methane or 2,2' -bis [4- (4-maleimidophenoxy) phenyl ] propane, the dielectric properties of the resin composition can be further improved. Taking bis (3-ethyl-5-methyl-4-maleimidophenyl) methane as an example, the structure is as follows:
from the molecular structure of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, it is known that the bismaleimide resin has a more hydrocarbon structure and thus is more excellent in dielectric properties.
Benzoxazine resins
The benzoxazine resin is a phenolic resin with heterocyclic structure synthesized by taking phenolic compounds, aldehydes and amine compounds as raw materials, and the phenolic resin is subjected to ring-opening polymerization under the action of heating and/or a catalyst to generate a nitrogen-containing phenolic resin-like net, has good heat resistance and flame retardance, does not release small molecules in the curing and forming process, and is a resin material with wide application prospect. However, the conventional benzoxazine resin has high modulus, large brittleness, poor toughness and easy generation of stress cracks on interfaces, so that the conventional benzoxazine resin is singly suitable for being used in copper-clad plates and easy to generate cracks.
The benzoxazine resin used in the present application is a benzoxazine resin containing a nitrile group, preferably a benzoxazine resin containing phthalonitrile. The nitrile group, the phenolic hydroxyl and the imine structure in the benzoxazine resin have synergistic effect in the polymerization of the monomers, so that the reaction rate can be improved, the reaction temperature can be reduced, the use of a catalyst is reduced, and the special reaction between the nitrile group and a Mannihc bridge can further improve the glass transition temperature and the heat resistance of the cured polymer.
Specifically, the benzoxazine resin containing nitrile groups used in the present application may be a benzoxazine resin having the following structure:
a formula I;
a formula II;
wherein n is an integer of 0 to 10.
Further preferably, the weight average molecular weight range of the nitrile group-containing dicyclopentadiene type benzoxazine resin is 1000-10000, the molecular weight distribution coefficient is 1.0-4.0, and the softening point is 100-160 ℃; more preferably, the weight average molecular weight range is 2000-5000, the molecular weight distribution coefficient is 1.5-3.0, and the softening point is 110-150 ℃; the polymer obtained by curing the polymer has excellent comprehensive performance, and the appearance of the finished product of the pressing plate is better.
In addition, the resin monomer comprises bismaleimide resin, benzoxazine resin containing nitrile groups and epoxy resin, and in order to achieve better dielectric property, the dosage of the benzoxazine resin containing nitrile groups is not too high, because the dielectric property index of the benzoxazine resin containing nitrile groups is slightly worse than that of bismaleimide; therefore, the amount of the benzoxazine resin containing nitrile groups is not higher than that of the bismaleimide resin when the resin is used. In addition, the amount of the benzoxazine resin containing nitrile groups is preferably not less than the amount of the epoxy resin because the epoxy resin is inferior in heat resistance, low in glass transition temperature and poor in dimensional stability, and thus is not preferable to be excessively added.
Epoxy resin
The epoxy resin used in the application is a phosphorus-free and halogen-free resin containing at least one epoxy group monomer, and can be any one or a mixture of at least two of phenolic epoxy resin, biphenyl epoxy resin, naphthol epoxy resin, dicyclopentadiene epoxy resin and multifunctional epoxy resin; preferably any one or a mixture of at least two of dicyclopentadiene type epoxy resin or naphthol type epoxy resin; still more preferred is a naphthol type epoxy resin. The naphthol type epoxy resin contains two benzene rings sharing double bonds, so that the high symmetry of a molecular structure is improved; in particular, for naphthol-type epoxy resins having an even number of epoxy groups, such as four epoxy groups, the naphthol-type epoxy resin has high symmetry, high rigidity and low viscosity, which is advantageous for increasing the crosslinking density and glass transition temperature of the epoxy resin.
[ curing agent ]
The curing agent is any one or a mixture of two of anhydride curing agents and amine curing agents. Dicyandiamide curing agents are preferred. The specific amount is a conventional amount for curing the resin, and the amount of the curing agent can be appropriately reduced, and for example, 1 to 5 parts by mass of the curing agent, preferably 1 to 3 parts by mass, can be used based on 100 parts by mass of the resin.
Preferably, in order to further improve the curing efficiency, reduce the curing temperature and optimize the curing process, a small amount of a curing accelerator such as any one or a combination of at least two of imidazole curing accelerators, triphenylphosphine or boron trifluoride monoethylamine may be added to the resin dope. Preferably 2-ethyl-4-methylimidazole. The curing accelerator is used in an amount of 0.1 to 2.0 parts by mass, preferably 0.5 to 1.5 parts by mass, based on 100 parts by mass of the resin.
[ Filler ]
In order to improve the molding property of the resin glue solution, improve the glass transition temperature, the dimensional stability, the mechanical property, the electrical property and the cost of the copper-clad plate, and inorganic filler is also added into the resin glue solution for forming the prepreg. Wherein, the inorganic filler can be any one or a mixture of at least two of barium sulfate, talcum powder, crystalline silicon dioxide, fused silicon dioxide, amorphous silicon dioxide, spherical silicon dioxide, nano silicon dioxide, magnesium carbonate, calcium carbonate, nano calcium carbonate, aluminum oxide, aluminum hydroxide or silicon micropowder. Spherical silica or modified silica is preferred. The modifying group in the modified silicon dioxide can be selected according to performance requirements to change the performance of the inorganic filler, such as hydrophilicity, hydrophobicity, heat resistance and the like, so as to improve the hydrophilicity, hydrophobicity, heat resistance and the like of the copper-clad plate.
Wherein the median particle diameter of the filler is 0.01-50 mu m, preferably 0.01-20 mu m; the addition amount of the resin composition is 50-200 parts by mass of inorganic filler, preferably 80-150 parts by mass, based on 100 parts by mass of the resin, so that the solid content of the resin glue solution formed by the resin composition is 50% -70%, the moldability of the resin glue solution is ensured, and the performances such as heat resistance and strength of the copper-clad plate are improved.
[ solvent ]
The solvent is one or a mixture of at least two of ketone, ester, ether or alcohol, such as one or a mixture of at least two of acetone, butanone, cyclohexanone, propylene glycol methyl ether, dimethylformamide and dimethylacetamide. Preferably dimethylformamide. The resin composition is used in an amount of 50 to 300 parts by mass, preferably 80 to 200 parts by mass, based on 100 parts by mass of the resin, so that the solid content of the resin glue solution formed by the resin composition is 50 to 70%, and the moldability of the resin glue solution is ensured.
[ others ]
In some embodiments, a certain amount of flame retardant can be added into the resin composition and the resin glue solution thereof provided by the application, so that the flame retardant property of the obtained copper-clad plate is further improved. Wherein the flame retardant can be any one or a mixture of two of phosphate and a compound thereof or a phenoxyphosphazene compound. Further, resorcinol bis (2, 6-dimethylphenyl) phosphate is preferred. The amount of the flame retardant is 0 to 30 parts by mass, preferably 0 to 10 parts by mass, based on 100 parts by mass of the resin.
The application also provides a prepreg comprising a reinforcing material and an attachment attached to the reinforcing material; the attachment is obtained by curing the resin composition according to the first aspect or the resin dope according to the second aspect.
In some embodiments, the reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics. The natural fiber, the organic synthetic fiber, the organic fabric and the inorganic fabric may be any fiber or fabric that may be used for the copper-clad plate, which is not an improvement point of the present application, and thus will not be described in detail in the present application.
[ preparation Process ]
The resin glue solution provided by the application is prepared by mixing a resin composition according to a given formula, and the mixing time can be adjusted according to the components such as the added inorganic filler, solvent and the like, and the adopted dispersing means and dispersing rate. The dispersing means can be mechanical stirring, magnetic stirring and the like.
The preparation process of the prepreg comprises an impregnation process and a curing process; the impregnation process comprises the steps of impregnating a reinforcing material in a resin glue solution, and keeping the impregnation for 0.5-1min to enable components in the resin glue solution to enter the reinforcing material; the curing process comprises the following steps: and (3) carrying out heat treatment on the reinforcing material attached with the resin composition or the resin glue solution for 1-10min at the temperature of 100-200 ℃ to crosslink, cure and form the resin monomer in the resin glue solution.
The electric copper-clad plate comprises a prepreg and a copper foil, and the preparation process comprises a copper-clad process and a lamination process. The copper foil coating process comprises the steps of coating copper foil on one side or two sides of a prepreg to form a semi-finished device; the lamination process comprises the following steps: firstly, raising the temperature to 170-190 ℃ at a heating rate of 4-6 ℃/min, raising the temperature to 5MPa at a rate of 0.05-0.2 MPa/min, and pressing the semi-finished device for 2-4 h; and pressing the semi-finished device for 2-6 hours at 200-240 ℃ and 5MPa to obtain the electric copper-clad plate.
The above-mentioned halogen-free flame retardant high Tg resin composition, resin glue solution, prepreg, electric copper-clad plate, and preparation method thereof, and circuit board of the present application will be described below with reference to specific examples, which should be understood by those skilled in the art to be merely helpful in understanding the present invention, and should not be construed as being a specific limitation of the present application. The specific techniques or conditions are not identified in the examples, and the reagents or apparatus used, which are conventional products available commercially, are carried out according to conventional techniques or conditions in the art or according to the specifications of the product, and the manufacturer is not identified.
The benzoxazines containing nitrile groups used in the following specific examples were all purchased from Chengdu Corp. High molecular technology Co., ltd;
the bismaleimide resin used in the following specific examples was purchased from KI company under the brand name KI-70;
the epoxy resins used in the following specific examples were purchased from Kaiyin chemical Co., ltd. Shanghai;
the 2-ethyl-4-methylimidazole used in the following examples was purchased from Shanghai Michlin Biochemical technologies Co., ltd;
dicyandiamide used in the following specific examples was purchased from kappaphycus alvarezii chemical industry limited;
the flame retardant resorcinol bis (2, 6-dimethylphenyl) phosphate used in the following specific examples was purchased from Daba chemical industry under the trade designation PX-200;
the spherical silica used in the following specific examples was purchased from Colon Chemicals, inc. of Chemicals, chemie, inc., chemie, co., ltd.
The solvent Dimethylformamide (DMF) used in the following specific examples was purchased from Colon Chemicals Co., ltd.
Example 1
The embodiment provides an electric copper-clad plate, which comprises a prepreg and a copper foil, wherein the preparation of the prepreg comprises the following steps:
taking 150g of bismaleimide resin KI-70 and 3g of dicyandiamide in a mixing container, adding 271g of solvent DMF, controlling the temperature at 50 ℃, fully stirring to enable the solvent DMF to be completely dissolved, sequentially adding 72g of naphthol epoxy resin NC-7300L 61g, 72g of nitrile group-containing DCPD-type benzoxazine resin, 300g (D50 mu m) of spherical silica and 100 g-200 g of PX-16 g, and finally adding 3.4g of 2-ethyl-4-methylimidazole, 500rad/min and stirring for 4h to obtain a glue solution of the resin composition, wherein the solid content of the glue solution is 68%.
And (3) taking glass fiber cloth with a proper size, impregnating the glass fiber cloth with the composition, and baking for 6min at 170 ℃ in a blast drying oven to fully volatilize the solvent to obtain the prepreg.
The electric copper-clad plate is prepared from the prepreg, and the specific preparation steps are as follows:
and (3) covering the obtained 5 prepregs with copper foil, pressing and forming in a vacuum press, heating from room temperature to 180 ℃ at a heating rate of 4 ℃/min, heating from 0.5MPa to 5MPa at a speed of 0.1MPa/min, and keeping pressing for 2 hours. And heating to 230 ℃, keeping pressing for 2 hours, releasing pressure and naturally cooling to obtain the electric copper-clad plate.
Example 2
The embodiment provides an electric copper-clad plate, which comprises a prepreg and a copper foil, wherein the preparation of the prepreg comprises the following steps:
taking 150g of bismaleimide resin KI-70 and 4g of dicyandiamide in a mixing container, adding 271g of solvent DMF, controlling the temperature to be 50 ℃, fully stirring to enable the solvent DMF to be fully dissolved, sequentially adding 72g of DCPD epoxy resin HP-7200H 61g, 72g of nitrile group-containing DCPD-benzoxazine resin, 300g of spherical silica and 200-16 g of PX, finally adding 3.4g of 2-ethyl-4-methylimidazole, fully stirring for 4h, and obtaining a glue solution of the resin composition, wherein the solid content of the glue solution is 68%.
And (3) taking glass fiber cloth with a proper size, impregnating the glass fiber cloth with the composition, and baking for 6min at 170 ℃ in a blast drying oven to fully volatilize the solvent to obtain the prepreg.
The electric copper-clad plate is prepared from the prepreg, and the specific preparation steps are as follows:
and (3) covering the obtained 5 prepregs with copper foil, pressing and forming in a vacuum press, heating from room temperature to 180 ℃ at a heating rate of 4 ℃/min, heating from 0.5MPa to 5MPa at a speed of 0.1MPa/min, and keeping pressing for 2 hours. And heating to 230 ℃, keeping pressing for 2 hours, releasing pressure and naturally cooling to obtain the electric copper-clad plate.
Example 3
The embodiment provides an electric copper-clad plate, which comprises a prepreg and a copper foil, wherein the preparation of the prepreg comprises the following steps:
taking 150g of bismaleimide resin KI-70 and 3g of dicyandiamide in a mixing container, adding 300g of solvent DMF, controlling the temperature at 50 ℃, fully stirring to enable the solvent DMF to be fully dissolved, sequentially adding 72g of naphthol epoxy resin NC-7300L 61g, 72g of nitrile group-containing phenolphthalein type benzoxazine resin, 300g of spherical silicon dioxide and 100 g of PX-200 16g, and finally adding 3.4g of 2-ethyl-4-methylimidazole, fully stirring for 5h to obtain a glue solution of the resin composition, wherein the solid content of the glue solution is 66%.
And (3) taking glass fiber cloth with a proper size, impregnating the glass fiber cloth with the composition, and baking for 6min at 170 ℃ in a blast drying oven to fully volatilize the solvent to obtain the prepreg.
The electric copper-clad plate is prepared from the prepreg, and the specific preparation steps are as follows:
and (3) covering the obtained 5 prepregs with copper foil, pressing and forming in a vacuum press, heating from room temperature to 180 ℃ at a heating rate of 4 ℃/min, heating from 0.5MPa to 5MPa at a speed of 0.1MPa/min, and keeping pressing for 2 hours. And heating to 230 ℃, keeping pressing for 2 hours, releasing pressure and naturally cooling to obtain the copper-clad plate.
Example 4
The embodiment provides an electric copper-clad plate, which comprises a prepreg and a copper foil, wherein the preparation of the prepreg comprises the following steps:
taking 150g of bismaleimide resin KI-70 g and 4g of dicyandiamide in a mixing container, adding 300g of solvent, controlling the temperature at 50 ℃, fully stirring to enable the bismaleimide resin KI-70 g and the dicyandiamide to be completely dissolved, sequentially adding 72g of DCPD epoxy resin HP-7200H 61g, 72g of nitrile group-containing phenolphthalein type benzoxazine resin, 300g of spherical silicon dioxide and 200-16 g of PX, and finally adding 4.2g of 2-ethyl-4-methylimidazole, fully stirring for 4h to obtain a glue solution of the resin composition, wherein the solid content of the glue solution is 66%.
And (3) taking glass fiber cloth with a proper size, impregnating the glass fiber cloth with the composition, and baking for 6min at 170 ℃ in a blast drying oven to fully volatilize the solvent to obtain the prepreg.
The electric copper-clad plate is prepared from the prepreg, and the specific preparation steps are as follows:
and (3) covering the obtained 5 prepregs with copper foil, pressing and forming in a vacuum press, heating from room temperature to 180 ℃ at a heating rate of 4 ℃/min, heating from 0.5MPa to 5MPa at a speed of 0.1MPa/min, and keeping pressing for 2 hours. And heating to 230 ℃, keeping pressing for 2 hours, releasing pressure and naturally cooling to obtain the copper-clad plate.
Example 5
The embodiment provides an electric copper-clad plate, which comprises a prepreg and a copper foil, wherein the preparation of the prepreg comprises the following steps:
taking 150g of bismaleimide resin KI-70 and 2.50g of dicyandiamide in a mixing container, adding 500g of solvent DMF, controlling the temperature at 50 ℃, fully stirring to enable the solvent DMF to be completely dissolved, sequentially adding 72g of naphthol epoxy resin NC-7300L 61g, 72g of nitrile group-containing DCPD-type benzoxazine resin, 400g of spherical silica, and finally adding 4.5g of 2-ethyl-4-methylimidazole, and fully stirring for 4 hours to obtain a glue solution of the resin composition, wherein the solid content of the glue solution is 57%.
And (3) taking glass fiber cloth with a proper size, impregnating the glass fiber cloth with the composition, and baking for 6min at 170 ℃ in a blast drying oven to fully volatilize the solvent to obtain the prepreg.
The electric copper-clad plate is prepared from the prepreg, and the specific preparation steps are as follows:
and (3) covering the obtained 5 prepregs with copper foil, pressing and forming in a vacuum press, heating from room temperature to 180 ℃ at a heating rate of 4 ℃/min, heating from 0.5MPa to 5MPa at a speed of 0.1MPa/min, and keeping pressing for 2 hours. And heating to 230 ℃, keeping pressing for 2 hours, releasing pressure and naturally cooling to obtain the copper-clad plate.
Comparative example 1
This comparative example was different from example 5 in that the solvent was added in an amount of 271g, and a resin dope having a solid content of 71% was obtained by the same procedure as in example 5; the remaining procedure was the same as in example 5 to obtain comparative product 1.
Comparative example 2
The comparative example is different from example 5 in that the bismaleimide resin KI-70 was added in an amount of 150g and the naphthol epoxy resin NC-7300L was added in an amount of: 22g of a nitrile group-containing DCPD-type benzoxazine resin with the addition amount of 20g, and obtaining a resin glue solution with the solid content of 68% by adopting the same procedure as in example 5; the remaining procedure was the same as in example 5 to obtain comparative product 2.
Comparative example 3
The comparative example is different from example 5 in that the amount of bismaleimide resin KI-70 added is 50g and the amount of naphthol epoxy resin NC-7300L added is: 40g of nitrile group-containing DCPD-type benzoxazine resin with the addition amount of 150g is prepared into resin glue solution with the solid content of 69% by adopting the same procedure as in example 5; the remaining procedure was the same as in example 5 to obtain comparative product 3.
Comparative example 4
This comparative example was different from example 5 in that the bismaleimide resin was replaced with polyphenylene ether resin SA9000, and a resin dope having a solid content of 57% was obtained by the same procedure as in example 5; the remaining procedure was the same as in example 5 to obtain comparative product 4.
Comparative example 5
This comparative example was compared with example 5, except that naphthol epoxy resin NC-7300L was replaced with bisphenol A epoxy resin NPEL-128, and the same procedure as in example 5 was used to obtain a resin dope having a solid content of 57%; the remaining procedure was the same as in example 5 to obtain comparative product 5.
Comparative example 6
This comparative example was different from example 5 in that the nitrile group-containing DCPD-type benzoxazine resin was replaced with a nitrile group-containing bisphenol A-type benzoxazine resin, and a resin dope having a solid content of 57% was obtained by the same procedure as in example 5; the remaining procedure was the same as in example 5 to obtain comparative product 6.
Comparative example 7
This comparative example is different from example 5 in that the nitrile group-containing DCPD-type benzoxazine resin was replaced with a nitrile group-containing bisphenol A-type benzoxazine resin, and PX-200 16g was added; the amount of 2-ethyl-4-methylimidazole added was 3.40g, and the same procedure as in example 5 was followed to obtain a resin dope having a solid content of 58%; the remaining procedure was the same as in example 5 to obtain comparative product 7.
Comparative example 8
The comparative example was different from example 5 in that the benzoxazine resin used was a nitrile group-containing bisphenol F-type benzoxazine resin, the addition amount of spherical silica was 330g and PX-200 g was added, simultaneously, the addition amount of dicyandiamide was 2.75g, the addition amount of solvent was 338g, the addition amount of 2-ethyl-4-methylimidazole was 4.32g, and the same procedure as in example 5 was adopted to obtain a resin dope, the solid content of which was 64%; the remaining procedure was as in example 5 to give comparative product 8.
Comparative example 9
This comparative example was different from example 5 in that the benzoxazine resin used was a DCPD type benzoxazine resin, the addition amount of spherical silica was 300g and PX-200 16g was added, the addition amount of solvent was 271g, the addition amount of 2-ethyl-4-methylimidazole was 3.4g, and the same procedure as in example 5 was adopted to obtain a resin dope having a solid content of 68%; the remaining procedure was as in example 5 to give comparative product 9.
And (3) testing:
the electrical copper-clad plates obtained in examples 1 to 5 and comparative examples 1 to 9 were subjected to performance tests such as glass transition temperature, thermal decomposition temperature, thermal delamination time (T-288), dielectric constant, dielectric loss factor, thermal expansion coefficient and flame retardance, and the test methods were as follows:
(1) Thermal stratification time T-288: the measurement was carried out according to the method prescribed by IPC-TM-650.2.4.24;
(2) Dielectric constant (Dk): the measurement was performed according to the test method specified in IPC-TM-650.2.5.5.9;
(3) Dielectric loss factor (Df): the measurement was performed according to the test method specified in IPC-TM-650.2.5.5.9;
(4) Glass transition temperature (Tg): according to differential scanning calorimetry, the measurement was performed according to the DMA method specified in IPC-TM-650.2.4.25;
(5) Coefficient of Thermal Expansion (CTE) in the X/Y axis: the measurement is carried out according to a test method specified by IPC-TM-650.2.4.24, and the test interval is 30-200300 ℃;
(6) UL94 flame retardant performance test: measured according to the UL94 vertical burn test method.
The test results are shown in the following table 1,
TABLE 1
As can be seen from Table 1, the copper-clad plate has the characteristics of halogen-free flame retardance, the flame retardance grade can meet the UL 94V 0 grade, the glass transition temperature is high, the heat resistance and the welding resistance are excellent, and the CET is low.
The copper-clad plates provided in embodiments 1 to 5 of the present application all have higher glass transition temperature, longer thermal delamination time, lower thermal expansion coefficient and lower dielectric constant. Therefore, the resin composition provided by the application is beneficial to improving the glass transition temperature of the copper-clad plate and improving the heat resistance, and simultaneously reduces the dielectric constant and dielectric loss, so that the obtained copper-clad plate has better dielectric property and heat resistance, and can meet the requirements of the carrier-like plate field.
In comparative example 1, the fluidity was poor due to the too high solid content, and the pressed sheet had a phase separation phenomenon, resulting in poor T-288 of the obtained copper-clad laminate. In comparative examples 2 to 6, the index could not meet the requirements of the carrier-like board after changing the formulation. Meanwhile, compared with the nitrile group-containing bisphenol A and bisphenol F-type benzoxazine resins adopted in comparative examples 7-8, the nitrile group-containing DCPD benzoxazine resins and phenolphthalein benzoxazine resins adopted in examples 1-5 can effectively improve the glass transition temperature of the copper-clad plate, and the copper-clad plate has lower dielectric constant and dielectric loss factor, so that the obtained copper-clad plate can have both temperature resistance and dielectric property. Therefore, the DCPD benzoxazine resin and the phenolphthalein benzoxazine resin containing nitrile groups have positive effects on improving the glass transition temperature and the dielectric property of the copper-clad plate. In addition, for examples 1 and 5, it can be seen that the benzoxazine containing nitrile group has good flame retardancy, and the prepared copper-clad plate still has V-0 flame retardant grade even under the condition of no flame retardant.
In conclusion, the prepared copper-clad plate has the characteristics of halogen-free flame retardance, the flame retardance grade can meet the UL 94V-0 grade, the glass transition temperature is high, the heat resistance is excellent, and the requirements of the carrier-like plate field can be met.
The present invention is not limited to the above embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims (15)

1. A halogen-free flame retardant high Tg resin composition comprising a resin, a curing agent, a filler, and a solvent, wherein the resin comprises a bismaleimide resin, a benzoxazine resin, and an epoxy resin;
wherein the benzoxazine resin is benzoxazine resin containing nitrile groups and the nitrile groups are end groups; the bismaleimide resin is any one or a combination of at least two of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3, 5-diethyl-4-maleimidophenyl) methane, bis (3, 5-dimethyl-4-maleimidophenyl) methane or 2,2' -bis [4- (4-maleimidophenoxy) phenyl ] propane;
wherein the benzoxazine resin is selected from one or a combination of at least two compounds shown in the following structural formula:
a formula I;
a formula II;
wherein n in the formula I is an integer of 0-10;
the epoxy resin is halogen-free and phosphorus-free epoxy resin, and is selected from any one or a mixture of at least two of phenolic epoxy resin, biphenyl epoxy resin, naphthol epoxy resin and dicyclopentadiene epoxy resin;
the mass ratio of the bismaleimide resin to the benzoxazine resin to the epoxy resin is 60 (10-50): 10-40;
the resin composition comprises the following components in parts by mass:
100 parts of resin
1-5 parts of curing agent
50-200 parts of filler
50-300 parts of solvent.
2. The halogen-free flame-retardant high Tg resin composition according to claim 1, wherein the mass ratio of the bismaleimide resin, the benzoxazine resin and the epoxy resin is 60 (20-35): 20-30.
3. The halogen-free flame retardant high Tg resin composition according to claim 1, wherein said benzoxazine resin is a dicyclopentadiene type benzoxazine resin containing nitrile groups.
4. The halogen-free flame retardant high Tg resin composition according to claim 1, wherein said benzoxazine resin is a nitrile group-containing dicyclopentadiene type benzoxazine resin having a weight average molecular weight of 1000 to 10000, and wherein said benzoxazine resin has a molecular weight distribution coefficient of 1.0 to 4.0 and a softening point of 100 to 160 ℃.
5. The halogen-free flame retardant high Tg resin composition according to claim 1, wherein said curing agent is selected from any one or a mixture of two of an acid anhydride curing agent and an amine curing agent; and/or
The filler is any one or a mixture of at least two of barium sulfate, talcum powder, crystalline silicon dioxide, amorphous silicon dioxide, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide or silicon micropowder; and/or
The solvent is any one or a mixture of at least two of ketone, ester, ether or alcohol.
6. A resin glue solution formulated from the halogen-free flame retardant high Tg resin composition according to any one of claims 1 to 5.
7. The resin glue solution according to claim 6, wherein the solid content of the resin glue solution is 50% -70%.
8. A prepreg comprising a reinforcing material and an attachment attached to the reinforcing material; the deposit is obtained by curing the resin composition according to any one of claims 1 to 5 or the resin dope according to any one of claims 6 to 7.
9. The prepreg of claim 8, wherein the reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics.
10. The method for preparing the prepreg according to claim 8 or 9, comprising the steps of:
providing a reinforcing material, the resin composition of any one of claims 1 to 5 or the resin dope of any one of claims 6 to 7;
and enabling the resin composition or the resin glue solution to be attached to the surface of the reinforcing material and semi-curing the resin composition or the resin glue solution to obtain the prepreg.
11. The method for preparing a prepreg according to claim 10, wherein adhering a resin composition or a resin glue solution to the surface of the reinforcing material and semi-curing the resin composition or the resin glue solution comprises:
impregnating the reinforcing material with the resin composition for 0.5-1min;
heat treating the reinforcing material with the resin composition or resin glue solution at 100-200deg.C for 1-10min.
12. An electric copper-clad plate is characterized by comprising the prepreg according to claim 8 or 9 or the prepreg prepared by the preparation method of the prepreg according to claim 10 or 11.
13. The electrical copper-clad plate of claim 12, wherein the electrical copper-clad plate further comprises a copper foil; copper foil is coated on one side or both sides of the prepreg.
14. The electrical copper-clad plate according to claim 12, wherein the electrical copper-clad plate has a glass transition temperature of not lower than 290 ℃, a dielectric constant of not higher than 4, a dielectric loss of not higher than 0.007, and an X/Y axis thermal expansion coefficient of not higher than 7 ppm/°c at a temperature of 30-300 ℃.
15. A circuit board comprising the electrical copper-clad plate of any one of claims 12 to 14.
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