CN112266572A - Resin composition, prepreg, laminate, and circuit board - Google Patents

Resin composition, prepreg, laminate, and circuit board Download PDF

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CN112266572A
CN112266572A CN202011177408.8A CN202011177408A CN112266572A CN 112266572 A CN112266572 A CN 112266572A CN 202011177408 A CN202011177408 A CN 202011177408A CN 112266572 A CN112266572 A CN 112266572A
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resin composition
parts
resin
benzoxazine
styrene
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CN112266572B (en
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杨宋
马建
熊峰
崔春梅
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Suzhou Shengyi Technology Co Ltd
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Suzhou Shengyi Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention provides a resin composition, which comprises a phosphorus-containing double-bond-containing benzoxazine resin, so that a cured product has excellent low dielectric constant, low dielectric loss, halogen-free flame retardance, moist heat resistance and higher glass transition temperature; the invention also provides a prepreg, a laminated board and a circuit substrate which are prepared by using the resin composition.

Description

Resin composition, prepreg, laminate, and circuit board
Technical Field
The invention relates to the technical field of electronic materials, in particular to a resin composition, a prepreg prepared from the resin composition, a laminated board and a circuit substrate.
Background
In the prior art, a halogen flame retardant is generally adopted in a laminated board for a circuit substrate to achieve the purpose of flame retardance, however, the halogen flame retardant generates strongly corrosive halogenated gas in the combustion process, and the halogen flame retardant generates carcinogens such as dioxin, dibenzofuran and the like in pyrolysis and combustion according to literature reports. Since the official implementation of the directive on scrapping of electrical and electronic devices and the directive on limiting the use of hazardous substances in electrical and electronic devices issued in the european union, the development of laminates for halogen-free flame-retardant circuit boards has become a major research and development point in the industry.
At present, phosphorus-containing compounds are used to replace the conventional bromine flame retardants in the commonly adopted method in the industry, but the products of the phosphorus-containing compounds generally have the problems of insufficient tin immersion heat resistance, easy moisture absorption, insufficient tin immersion heat resistance after moisture treatment and the like.
With the recent increase in the speed and frequency of information processing and information transmission, a laminate for a circuit board has been required to have higher dielectric properties. In short, the laminate material needs to have low dielectric constant and dielectric loss to reduce the delay, distortion and loss of signals in high-speed transmission and the interference between signals. However, epoxy resins have high dielectric constants and dielectric losses, and are difficult to meet high frequency applications.
On the basis of the traditional method for preparing phenolic resin, benzoxazine is subjected to cyclization reaction through primary amine, phenol and aldehyde to obtain a benzoxazine intermediate, under the condition of heating or a catalyst, benzoxazine is subjected to ring opening to generate a novel thermosetting resin with a net structure, a cured product of the benzoxazine has high glass transition temperature, the decomposition temperature is less than 1% when reaching 350 ℃, and in addition, the benzoxazine contains nitrogen elements, so that the benzoxazine has good flame retardance. However, benzoxazines do not exhibit sufficient flame retardant effect and require the addition of additives such as bromine, phosphorus or chlorine compounds. These additives affect the processability of copper clad laminates and have poor oxidation stability and physical properties at high temperatures.
In view of the above, there is a need to provide a novel resin composition, a prepreg, a laminate and a circuit substrate prepared therefrom to solve the above problems.
Disclosure of Invention
The invention aims to provide a resin composition which can simultaneously meet the requirements of non-halogenation and high frequency, and a prepreg, a laminated board and a circuit substrate prepared from the resin composition. The prepreg, the laminated board and the circuit substrate have excellent low dielectric constant, low dielectric loss, halogen-free flame retardance, moist heat resistance and higher glass transition temperature.
In order to achieve the purpose, the invention adopts the following technical scheme: a resin composition comprising, by weight:
a crosslinking agent: 1-80 parts;
benzoxazine resin: 5-80 parts;
the benzoxazine resin comprises at least one of the following structural formulas:
Figure BDA0002749096760000021
structural formula (1);
Figure BDA0002749096760000022
structural formula (2);
Figure BDA0002749096760000031
structural formula (3);
Figure BDA0002749096760000032
structural formula (4);
Figure BDA0002749096760000033
structural formula (5);
wherein, R1, R2, R3 and R4 are the same or different and are respectively selected from hydrogen, methyl, ethyl, propyl or tert-butyl; r is methyl, ethyl, phenyl, vinyl, allyl, styryl, allyl,
Figure BDA0002749096760000034
at least one R group in each formula is a group containing an unsaturated double bond; x is phenyl or methylA radical or an ethyl radical.
Further, the crosslinking agent has an unsaturated double bond; the crosslinking agent is polybutadiene, modified polybutadiene, polypentadiene, modified polypentadiene, polyisoprene, modified polyisoprene, polystyrene, butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, hydrogenated diene-butadiene-styrene copolymer, maleic anhydride diene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene-divinylbenzene copolymer, maleic anhydride styrene-butadiene copolymer, cyclopentadiene, modified cyclopentadiene, dicyclopentadiene, modified dicyclopentadiene, styrene-pentadiene copolymer, styrene-polypentadiene copolymer, butadiene-cyclopentadiene copolymer, ethylene-cyclopentadiene copolymer, polyisoprene, isoprene-butadiene copolymer, styrene-isoprene copolymer, isoprene-, At least one of norbornene polymer, modified norbornene polymer, divinylbenzene, bis (vinylbenzyl) ether, bis (vinylphenyl) ethane, divinylbiphenyl, polyphenylene ether having double bonds, maleimide, cyanate ester having double bonds, and phenol resin having double bonds.
Further, the resin composition comprises 10-60 parts of benzoxazine resin and 5-70 parts of maleimide by weight.
Further, the resin composition further comprises a crosslinking assistant; the crosslinking assistant is at least one of triallyl isocyanate monomer, triallyl isocyanate monomer prepolymer, butadiene monomer, styrene monomer, pentadiene monomer, norbornene monomer or cyclopentadiene monomer.
Further, the resin composition comprises, by weight, 20-60 parts of benzoxazine resin, 5-60 parts of polyphenylene oxide containing double bonds and 5-60 parts of triallyl isocyanate monomer.
Further, the benzoxazine resin also includes benzoxazine resins other than structural formulas (1) to (5); the benzoxazine resin except the structural formulas (1) to (5) is at least one of bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, bisphenol S type benzoxazine resin or bisphenol E type benzoxazine resin.
Further, the content of the benzoxazine resin shown in structural formulas (1) to (5) is 10 to 100 parts by weight and the content of the benzoxazine resin except for the structural formulas (1) to (5) is 1 to 40 parts by weight based on 100 parts by weight of the benzoxazine resin.
Further, the resin composition also comprises a flame retardant, and/or an initiator, and/or a catalyst, and/or a filler, and/or an auxiliary agent, wherein the auxiliary agent comprises at least one of a coupling agent, a dispersing agent and a dye.
In order to achieve the above object, the present invention further provides a prepreg, characterized in that: and soaking the reinforcing material in the glue solution of the resin composition, and then heating and drying to form a prepreg.
In order to achieve the above object, the present invention further provides a laminate, which is formed by laminating a metal foil on at least one surface of one prepreg or at least two prepregs stacked one on another and thermally pressing the prepreg or the prepregs.
In order to achieve the above object, the present invention further provides a circuit substrate, which includes at least one prepreg or at least one laminated board.
Compared with the prior art, the invention has the following advantages:
in the resin composition, the benzoxazine resin containing phosphorus and alkene is matched with the cross-linking agent, namely, double bonds in the benzoxazine resin react with the cross-linking agent to obtain the resin composition which simultaneously meets the non-halogenation requirement and the high-frequency requirement, so that a cured product with higher cross-linking density can be obtained, and the cured product has excellent low dielectric constant, low dielectric loss, halogen-free flame retardance and wet heat resistance; on the other hand, the phosphorus-containing and alkene-containing benzoxazine resin contains nitrogen and phosphorus, and phosphorus and nitrogen are synergistically flame-retardant, so that the flame retardant efficiency of a system is greatly improved, phosphorus groups can be well introduced into a cured product, and the dielectric property and the water absorption rate of the cured product are further improved on the basis of improving the heat resistance and the flame retardance of the cured product; meanwhile, the benzoxazine resin containing phosphorus and alkene has a large number of hydrogen bonds, so that the problems of poor adhesion, poor toughness and the like caused by few polar groups can be solved, and the adhesion and the toughness of a cured product are remarkably improved.
Particularly, when the cross-linking agent is maleimide, the benzoxazine resin containing phosphorus and alkylene is matched with the maleimide, so that the benzoxazine resin has more excellent toughness, heat resistance, flame retardance and dielectric property.
Detailed Description
While the following is a detailed description of the embodiments of the present invention, it should be noted that those skilled in the art can make various modifications and improvements without departing from the principle of the embodiments of the present invention, and such modifications and improvements are considered to be within the scope of the embodiments of the present invention.
The "comprising" and "containing" in the present specification mean that other components capable of imparting different characteristics to the resin composition may be contained in addition to the components.
The expression "based on 100 parts by weight of the resin composition" in the present specification means that the total amount of components other than the crosslinking assistant, flame retardant, initiator, catalyst, filler, and assistant is 100 parts by weight.
The invention provides a resin composition, which comprises the following components in percentage by weight:
a crosslinking agent: 1-80 parts;
benzoxazine resin: 5-80 parts;
the benzoxazine resin comprises at least one of the following structural formulas:
Figure BDA0002749096760000051
structural formula (1);
Figure BDA0002749096760000061
structural formula (2);
Figure BDA0002749096760000062
structural formula (3);
Figure BDA0002749096760000063
structural formula (4);
Figure BDA0002749096760000064
structural formula (5);
wherein, R1, R2, R3 and R4 in the structural formulas (1) to (3) are independent from each other, namely R1, R2, R3 and R4 are the same or different, and R1, R2, R3 and R4 are respectively selected from hydrogen, methyl, ethyl, propyl or tert-butyl; r is methyl, ethyl, phenyl, vinyl, allyl, styryl, allyl,
Figure BDA0002749096760000065
at least one R group in each formula is a group containing an unsaturated double bond; x is phenyl, methyl or ethyl.
The resin composition of the present invention does not contain an epoxy resin, and the final cured product can have more excellent dielectric properties.
Specifically, in one embodiment, R1, R2, R3 and R4 in the structural formulas (1) to (3) are the same and are all selected from hydrogen or methyl.
Further, the R group is selected from styryl, allyl benzene,
Figure BDA0002749096760000066
Figure BDA0002749096760000071
Further, the X group is phenyl or methyl.
Further, the benzoxazine resin also includes benzoxazine resins other than structural formulas (1) to (5).
In a specific embodiment, the benzoxazine resin other than structural formulas (1) to (5) is at least one of bisphenol a type benzoxazine resin, bisphenol F type benzoxazine resin, bisphenol S type benzoxazine resin, or bisphenol E type benzoxazine resin; of course, this is not a limitation.
Specifically, the content of the benzoxazine resins represented by the structural formulas (1) to (5) is 10 to 100 parts by weight based on 100 parts by weight of the benzoxazine resin.
The above-mentioned "the content of the benzoxazine resin represented by the structural formulae (1) to (5) is 10 to 100 parts by weight" means the content of the benzoxazine resin represented by the structural formulae (1) to (5) contained in the benzoxazine resin. That is, in the embodiment in which only the benzoxazine resin represented by structural formula (1) is included in the benzoxazine resin, "the content of the benzoxazine resin represented by structural formulae (1) to (5) is 10 to 100 parts by weight", which means that the content of the benzoxazine resin represented by structural formula (1) is 10 to 100 parts by weight; in the embodiment that the benzoxazine resin only includes benzoxazine resins represented by structural formulas (1) and (2), "the content of the benzoxazine resin represented by structural formulas (1) to (5) is 10 to 100 parts by weight", that is, the content of the benzoxazine resin represented by structural formulas (1) and (2) is 10 to 100 parts by weight, and so on, and thus, the description thereof is omitted.
Specifically, the content of the benzoxazine resin other than the structural formulas (1) to (5) is 1 to 40 parts by weight based on 100 parts by weight of the benzoxazine resin.
Further, the crosslinking agent has unsaturated double bonds to improve the reactivity of the crosslinking agent with the double bonds in the benzoxazine resin.
Specifically, the crosslinking agent is polybutadiene, modified polybutadiene, polypentadiene, modified polypentadiene, polyisoprene, modified polyisoprene, polystyrene, butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, hydrogenated diene-butadiene-styrene copolymer, maleic anhydride-diene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene-divinylbenzene copolymer, maleic anhydride-styrene-butadiene copolymer, cyclopentadiene, modified cyclopentadiene, dicyclopentadiene, modified dicyclopentadiene, styrene-pentadiene copolymer, styrene-polypentadiene copolymer, butadiene-cyclopentadiene copolymer, ethylene-cyclopentadiene copolymer, polyisoprene, isoprene, at least one of norbornene polymer, modified norbornene polymer, divinylbenzene, bis (vinylbenzyl) ether, bis (vinylphenyl) ethane, divinylbiphenyl, polyphenylene ether having double bonds, maleimide, cyanate ester having double bonds, and phenol resin having double bonds.
Preferably, the cross-linking agent is polybutadiene, wherein the content of 1 and 2-vinyl groups is more than 45%, so that the reactivity of the cross-linking agent and double bonds in the benzoxazine resin is further improved.
Further preferably, the crosslinking agent is polyphenylene ether containing double bonds, although not limited thereto.
Further, the polyphenylene ether containing double bonds is at least one of the following structures:
Figure BDA0002749096760000081
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure BDA0002749096760000082
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure BDA0002749096760000083
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure BDA0002749096760000084
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure BDA0002749096760000091
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure BDA0002749096760000092
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure BDA0002749096760000093
in the structural formula, a and b are the same or different, a and b are both integers of 1-10, and n is an integer (including 0) of 0-5;
Figure BDA0002749096760000094
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure BDA0002749096760000095
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure BDA0002749096760000096
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure BDA0002749096760000097
in the structural formula, a and b are the same or different, a and b are integers from 1 to 10, and n is an integer from 1 to 5;
still further preferably, the cross-linking agent is maleimide.
In a specific embodiment where the cross-linking agent is maleimide, the resin composition comprises 10 to 60 parts by weight of benzoxazine resin and 5 to 70 parts by weight of maleimide.
The maleimide is a compound having at least one maleimide group in its molecular structure.
Preferably, the maleimide is at least one of the following structures:
Figure BDA0002749096760000101
Figure BDA0002749096760000102
wherein R2 is hydrogen, methyl or ethyl, R1 is methylene, ethylene or
Figure BDA0002749096760000103
Figure BDA0002749096760000104
Figure BDA0002749096760000111
Wherein n is an integer of 1 to 10;
Figure BDA0002749096760000112
wherein n is an integer of 1 to 10;
Figure BDA0002749096760000113
wherein n is an integer of 1 to 10;
Figure BDA0002749096760000114
wherein n is an integer of 1 to 10.
Further, the resin composition also comprises 0.1 to 10 parts of crosslinking auxiliary agent based on 100 parts of the resin composition.
Specifically, the crosslinking assistant is at least one of a triallyl isocyanate monomer, a triallyl isocyanate monomer prepolymer, a butadiene monomer, a styrene monomer, a pentadiene monomer, a norbornene monomer, or a cyclopentadiene monomer.
In a specific embodiment of the resin composition including the crosslinking assistant, the resin composition includes, by weight, 20 to 60 parts of benzoxazine resin, 5 to 60 parts of polyphenylene ether containing double bonds, and 5 to 60 parts of triallyl isocyanate monomer.
Further, the resin composition also comprises 5-40 parts of flame retardant based on 100 parts of the resin composition so as to improve the flame retardance of a finally formed cured product.
The cured product in the present invention is understood to be a prepreg, an insulating film, a laminate, a circuit board, and the like.
Specifically, the flame retardant is selected from phosphorus-containing phenolic resin, phosphazene or modified phosphazene, phosphate ester, melamine cyanurate, polyorganosiloxane, DOPO-HQ, DOPO-NQ, phosphorus oxychloride,
Figure BDA0002749096760000121
(m is an integer of 1 to 5),
Figure BDA0002749096760000122
Or DPO.
Wherein the structural formula of DOPO is as follows:
Figure BDA0002749096760000123
the structural formula of the DOPO-HQ is as follows:
Figure BDA0002749096760000124
the structural formula of DOPO-NQ is as follows:
Figure BDA0002749096760000131
the above-mentioned
Figure BDA0002749096760000132
The structural formula of (A) is:
Figure BDA0002749096760000133
the above-mentioned
Figure BDA0002749096760000134
Has the structural formula
Figure BDA0002749096760000135
Further, the flame retardant is preferably a phosphorus-containing compound, the phosphorus-containing compound is preferably an additive phosphorus-containing compound, and specifically, the additive phosphorus-containing compound can be phosphazene, such as the trademark SPB-100; or selecting modified phosphazene, such as trade marks of BP-PZ, PP-PZ, SPCN-100, SPV-100 and SPB-100L; or is selected from
Figure BDA0002749096760000136
Or is selected from
Figure BDA0002749096760000137
Further, the resin composition further comprises 0.1-5 parts of an initiator based on 100 parts of the resin composition, wherein the initiator is used for opening double bonds in benzoxazine and a crosslinking agent so as to increase the reactivity of the benzoxazine and the double bonds in the crosslinking agent, obtain a tighter crosslinking network structure and improve the heat resistance of a cured product.
Specifically, the initiator is a free radical initiator selected from at least one of dicumyl peroxide, or 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, or t-butylcumyl peroxide, or di-t-butyl peroxide, or α, α' -bis (t-butylperoxy) diisopropylbenzene and 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexyne-3.
Further, the resin composition also contains 0.01 to 2 parts of catalyst based on 100 parts of the resin composition. The catalyst is selected from at least one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole and 1-cyanoethyl-2-methylimidazole.
Further, the resin composition may further include 20 parts to 100 parts of a filler based on 100 parts of the resin composition, but it is understood that the resin composition may or may not include the filler.
Specifically, the filler is at least one of an organic filler or an inorganic filler.
The inorganic filler is selected from one or a mixture of at least any two of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate or inorganic phosphorus.
Preferably, the inorganic filler is at least one selected from the group consisting of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.
Further, the filler is silicon dioxide, particularly spherical silicon dioxide subjected to surface treatment, so that the filler is easier to disperse and can prevent agglomeration, and meanwhile, the spherical silicon dioxide subjected to surface treatment has a low thermal expansion coefficient and can prevent the final product from warping.
Specifically, the surface treatment agent for treating the spherical silica is a silane coupling agent, such as an epoxy silane coupling agent or an aminosilane coupling agent.
The organic filler is at least one selected from polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder.
In addition, the filler has a particle size median value of 1 to 15 μm, such as 1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm, and specific values therebetween are limited by space and for the sake of brevity, and the invention is not intended to be exhaustive of the specific values included in the ranges.
Preferably, the particle size median value of the filler is 1-10 mu m, so that the filler is easier to disperse and better in agglomeration prevention effect.
Further, the resin composition may further comprise an auxiliary agent according to different requirements of the final product of the present invention, and it is understood that the resin composition may or may not contain the auxiliary agent according to different requirements of the final product, or a suitable auxiliary agent may be selected according to requirements.
In the embodiment that the resin composition contains the auxiliary, the content of the auxiliary is 0-5 parts by 100 parts by weight of the resin composition.
Specifically, the other auxiliary agents comprise coupling agents, dispersing agents and dyes. The coupling agent is a silane coupling agent, such as an epoxy silane coupling agent or an aminosilane coupling agent; the dispersant is an amino silane compound having an amino group and a hydrolyzable group or a hydroxyl group such as γ -aminopropyltriethoxysilane, N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane, an epoxy silane compound having an epoxy group and a hydrolyzable group or a hydroxyl group such as 3-acryloxypropyltrimethoxysilane, a vinyl silane compound having a vinyl group and a hydrolyzable group or a hydroxyl group such as γ -methacryloxypropyltrimethoxysilane, or a cationic silane coupling agent, and the dispersant can be Disperbyk-110, 111, 118, 180, 161, 2009, BYK-W996, W9010, or W903 manufactured by BYK, and the above symbols are product names; the dye is a fluorescent dye and a black dye, wherein the fluorescent dye is pyrazoline and the like, and the black dye is liquid or powdery carbon black, a pyridine complex, an azo complex, aniline black, black talcum powder, cobalt chromium metal oxide, azine or phthalocyanine and the like.
It is understood that the resin composition also comprises a proper amount of organic solvent, and the components of the resin composition and the organic solvent are mixed to form a resin composition glue solution for standby.
Specifically, the organic solvent may be selected from one or a combination of any of acetone, butanone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.
The amount of the organic solvent to be used in the present invention is not particularly limited. The amount of the solvent to be added is selected by a person skilled in the art from his or her own experience, as long as the viscosity of the resulting resin composition dope can be adjusted to a suitable viscosity for use.
The invention further provides a prepreg, which comprises a reinforcing material and any one of the resin compositions attached to the surface of the reinforcing material.
Specifically, the reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric; preferably, the reinforcing material is glass fiber cloth, and open fiber cloth or flat cloth is preferably used in the glass fiber cloth.
In addition, when the reinforcing material is a glass cloth, the glass cloth generally needs to be chemically treated to improve the bonding between the resin composition and the interface of the glass cloth. The main method of the chemical treatment is a coupling agent treatment, and the coupling agent is preferably epoxy silane or amino silane or the like to provide good water resistance and heat resistance.
The preparation method of the prepreg comprises the following steps: and (2) soaking the reinforcing material in the resin composition glue solution, then baking the soaked reinforcing material at the temperature of 50-170 ℃ for 1-10 min, and drying to obtain the prepreg.
The invention further provides a laminated board which comprises at least one prepreg and metal foil formed on at least one surface of the prepreg.
In an embodiment where the laminate includes at least two prepregs as described above, the laminate is formed by stacking the at least two prepregs, bonding the stacked prepregs together by heating and pressing, and then bonding a metal foil to one or both surfaces of the bonded prepregs by heating and pressing.
Specifically, the preparation steps of the laminated board are as follows: and coating a metal foil on one side or both sides of one prepreg, or coating a metal foil on one side or both sides of at least 2 prepregs after laminating, and carrying out hot press forming to obtain the laminated board.
The pressing conditions of the above laminate were: pressing for 2-4 hours under the pressure of 0.2-2 MPa and the temperature of 180-250 ℃.
Specifically, the number of prepregs is determined according to the thickness of a desired laminate.
The metal foil can be copper foil or aluminum foil, and the material is not limited; the thickness of the metal foil is not particularly limited, and may be set according to specific requirements, and may be 5 μm, 8 μm, 12 μm, 18 μm, 35 μm, or 70 μm.
Furthermore, the invention also provides a circuit substrate, wherein the circuit substrate comprises at least one prepreg or at least one laminated board.
The preparation method of the circuit substrate can adopt the existing process, and the details are not repeated.
The present invention will be described in detail with reference to specific examples; of course, it is to be understood that the embodiments of the present invention are not limited to these embodiments.
Examples 1 to 5 and comparative examples 1 to 3:
the components and contents of the resin compositions of examples 1 to 5 and comparative examples 1 to 3 are shown in the following table 1:
TABLE 1
Figure BDA0002749096760000171
Figure BDA0002749096760000181
Wherein, the structural formula of benzoxazine a in table 1 above is:
Figure BDA0002749096760000182
the reaction mechanism for preparing the benzoxazine A is shown as follows:
Figure BDA0002749096760000183
the structural formula of benzoxazine B in table 1 above is:
Figure BDA0002749096760000184
the reaction mechanism for preparing the benzoxazine B is shown as follows:
Figure BDA0002749096760000185
the structural formula of the benzoxazine C in table 1 above is:
Figure BDA0002749096760000186
the reaction mechanism for preparing the benzoxazine C is as follows:
Figure BDA0002749096760000187
the structural formula of the benzoxazine D in table 1 above is:
Figure BDA0002749096760000191
it can be seen that benzoxazine a, benzoxazine B, and benzoxazine C belong to the benzoxazine resin represented by the structural formula (2). The benzoxazine D does not belong to the benzoxazine resins represented by the structural formulae (1) to (5).
In addition, the information on the other components other than benzoxazine a, benzoxazine B, benzoxazine C, benzoxazine D referred to in table 1 above is shown in table 2 below:
TABLE 2
Components Detailed description of the invention
Polybutadiene B-1000 manufactured by Nippon Caoda
Polyphenylene ether Polyphenylene ether having double bond, PPE-2St, manufactured by Mitsubishi Japan
Maleimide MBI, KI formation system
Filler material Spherical silica
Initiator Dicumyl peroxide
Catalyst and process for preparing same 2-methylimidazole
The resin compositions of examples 1 to 5 and comparative examples 1 to 3 were prepared by a conventional method, specifically: according to the components and the corresponding content in the table 1, benzoxazine A, benzoxazine B, benzoxazine C, benzoxazine D, bisphenol A type benzoxazine, polybutadiene, polyphenyl ether, maleimide, phosphate, filler, initiator and catalyst are mixed by using a proper amount of organic solvent, emulsified by using a high-speed emulsifier, and uniformly dispersed and mixed to obtain a resin composition glue solution with the solid content of 65%, wherein the solid content of 65% is calculated by weight.
The resin composition dopes obtained in examples 1 to 5 and comparative examples 1 to 3 were respectively impregnated and coated on E glass cloth (2116, single weight 104 g/m)2) And then baked in an oven at 145 ℃ for 6min to obtain prepregs with 50% of resin content in examples 1-5 and comparative examples 1-2, respectively.
Sample laminates prepared for performance evaluation were evaluated:
(1) preparation of Metal foil-clad laminate
The prepregs with the resin content of 50% prepared in the above examples 1 to 5 and comparative examples 1 to 2 were placed one metal foil on each of the upper and lower sides, and pressed in a vacuum hot press to obtain metal foil laminates, respectively. The specific pressing process is pressing for 2 hours under the pressure of 1.5MPa and the temperature of 220 ℃.
The performance evaluation method comprises the following steps:
(1) dielectric constant (Dk)/dielectric loss (Df): network analyzer (SPDR) method;
(2) glass transition temperature (Tg): the Dynamic Mechanical Analysis (DMA) instrument is used for testing whether the system has phase separation, and generally two or more Tg's show that the system has poor compatibility and phase separation.
(3) Flame retardancy: the UL94V method is adopted.
(4) Moist heat resistance (PCT): 3 pieces of a metal-clad laminate sheet having a thickness of 0.80mm and a thickness of 10cm × 10cm and having metal foils removed on both sides were dried at 100 ℃ for 2 hours, then treated at 121 ℃ under 2 atmospheres using a Pressure Cooker test (Pressure Cooker test) machine for 3 hours, and then dipped in tin at 288 ℃ for 20 seconds, and visually observed whether or not there was any delamination. If there are 0, 1, 2, 3 blocks in the 3 blocks, the layering phenomena are respectively recorded as 0/3, 1/3, 2/3, 3/3.
The properties of the metal foil-clad laminates obtained using the prepregs of examples 1 to 5 and comparative examples 1 to 3 are shown in table 3 below.
TABLE 3
Figure BDA0002749096760000201
Figure BDA0002749096760000211
As can be seen from table 3, the laminate obtained by using the resin composition of the present invention has more excellent low dielectric constant, low dielectric loss, halogen-free flame retardancy, and wet heat resistance, and has a higher glass transition temperature.
In particular, as can be seen from the parallel comparison between example 1 and comparative example 1, example 1 has more excellent low dielectric constant, low dielectric loss, halogen-free flame retardancy, moist heat resistance, and higher glass transition temperature than comparative example 1; from the parallel comparison between example 3 and comparative example 2, it can be seen that example 3 has more excellent low dielectric constant, low dielectric loss, halogen-free flame retardancy, moist heat resistance, and higher glass transition temperature than comparative example 2; from the parallel comparison between example 4 and comparative example 3, it can be seen that example 4 has a lower dielectric constant, a lower dielectric loss, a halogen-free flame retardancy, a higher moist heat resistance, and a higher glass transition temperature than comparative example 3.
It should be understood that although the present description refers to embodiments, not every embodiment contains only a single technical solution, and such description is for clarity only, and those skilled in the art should make the description as a whole, and the technical solutions in the embodiments can also be combined appropriately to form other embodiments understood by those skilled in the art.
The above-listed detailed description is only a specific description of a possible embodiment of the present invention, and they are not intended to limit the scope of the present invention, and equivalent embodiments or modifications made without departing from the technical spirit of the present invention should be included in the scope of the present invention.

Claims (10)

1. A resin composition characterized by comprising, by weight:
a crosslinking agent: 1-80 parts;
benzoxazine resin: 5-80 parts;
the benzoxazine resin comprises at least one of the following structural formulas:
Figure FDA0002749096750000011
wherein R1, R2, R3 and R4 are the same or different and are respectively selected from hydrogen, methyl, ethyl, propyl or tert-butyl; r is methyl, ethyl, phenyl, vinyl, allyl, styryl, allyl,
Figure FDA0002749096750000012
at least one R group in each formula is a group containing an unsaturated double bond; x is phenyl, methyl or ethyl;
and/or, the benzoxazine resin is selected from at least one of the following structural formulas:
Figure FDA0002749096750000013
Figure FDA0002749096750000021
wherein, R is methyl, ethyl, phenyl, vinyl, allyl, styryl, allyl, allyl,
Figure FDA0002749096750000022
In each structural formulaAt least one R group is a group containing an unsaturated double bond; x is phenyl, methyl or ethyl.
2. The resin composition according to claim 1, characterized in that: the crosslinking agent has an unsaturated double bond; the crosslinking agent is polybutadiene, modified polybutadiene, polypentadiene, modified polypentadiene, polyisoprene, modified polyisoprene, polystyrene, butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, hydrogenated diene-butadiene-styrene copolymer, maleic anhydride diene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene-divinylbenzene copolymer, maleic anhydride styrene-butadiene copolymer, cyclopentadiene, modified cyclopentadiene, dicyclopentadiene, modified dicyclopentadiene, styrene-pentadiene copolymer, styrene-polypentadiene copolymer, butadiene-cyclopentadiene copolymer, ethylene-cyclopentadiene copolymer, polyisoprene, isoprene-butadiene copolymer, styrene-isoprene copolymer, isoprene-, At least one of norbornene polymer, modified norbornene polymer, divinylbenzene, bis (vinylbenzyl) ether, bis (vinylphenyl) ethane, divinylbiphenyl, polyphenylene ether having double bonds, maleimide, cyanate ester having double bonds, and phenol resin having double bonds.
3. The resin composition according to claim 2, characterized in that: comprises the following components in parts by weight:
benzoxazine resin: 10-60 parts;
maleimide: 5-70 parts.
4. The resin composition according to claim 1, characterized in that: the resin composition further comprises a crosslinking assistant; the crosslinking assistant is at least one of triallyl isocyanate monomer, triallyl isocyanate monomer prepolymer, butadiene monomer, styrene monomer, pentadiene monomer, norbornene monomer or cyclopentadiene monomer.
5. The resin composition according to claim 4, characterized in that: comprises the following components in parts by weight:
benzoxazine resin: 20-60 parts;
double bond-containing polyphenylene ether: 5-60 parts;
triallyl isocyanate monomer: 5-60 parts.
6. The resin composition according to claim 1, characterized in that: the benzoxazine resin also comprises benzoxazine resins except structural formulas (1) to (5); the benzoxazine resin except the structural formulas (1) to (5) is at least one of bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, bisphenol S type benzoxazine resin or bisphenol E type benzoxazine resin; the content of the benzoxazine resin shown in structural formulas (1) to (5) is 10 to 100 parts by weight based on 100 parts by weight of the benzoxazine resin, and the content of the benzoxazine resin except for the structural formulas (1) to (5) is 1 to 40 parts by weight.
7. The resin composition according to claim 1, characterized in that: the resin composition also comprises a flame retardant, and/or an initiator, and/or a catalyst, and/or a filler, and/or an auxiliary agent, wherein the auxiliary agent comprises at least one of a coupling agent, a dispersing agent and a dye.
8. A prepreg characterized in that: impregnating a reinforcing material into the glue solution of the resin composition according to any one of claims 1 to 7, and then heating and drying to form a prepreg.
9. A laminate, characterized by: and covering at least one side of one prepreg or at least two prepregs which are arranged in a stacked manner with a metal foil for hot pressing to form a laminated plate, wherein the prepreg is the prepreg according to claim 8.
10. A circuit substrate, characterized in that: comprising at least one prepreg according to claim 8 or comprising at least one laminate according to claim 9.
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