阅读说明：本技术 树脂组合物及具有其的半固化片、层压板、印制线路板 (Resin composition, and prepreg, laminated board and printed wiring board provided with same ) 是由 杨宋 焦锋 崔春梅 陈诚 马建 于 2019-10-11 设计创作，主要内容包括：本发明提供了一种树脂组合物及具有其的半固化片、层压板、印制线路板。所述树脂组合物,包括：碳氢树脂、交联助、阻燃剂；所述碳氢树脂中至少含有环氧改性碳氢树脂；所述阻燃剂中至少含有含磷化合物(I),所述含磷化合物(I)为含磷酸酐化合物。本发明所述的树脂组合物,通过含磷酸酐化合物和环氧改性碳氢树脂反应,将含磷原子很好地引入碳氢树脂的固化交联体系中,获得同时满足无卤阻燃和低介电常数、低介质损耗值的基板材料。(The invention provides a resin composition, and a prepreg, a laminated board and a printed circuit board with the resin composition. The resin composition includes: hydrocarbon resin, crosslinking assistant and flame retardant; the hydrocarbon resin at least contains epoxy modified hydrocarbon resin; the flame retardant at least contains a phosphorus-containing compound (I), and the phosphorus-containing compound (I) is a phosphorus-containing anhydride compound. According to the resin composition, phosphorus-containing atoms are well introduced into a curing and crosslinking system of the hydrocarbon resin through the reaction of the phosphorus-containing anhydride compound and the epoxy modified hydrocarbon resin, so that the substrate material which simultaneously meets halogen-free flame retardance, low dielectric constant and low dielectric loss value is obtained.)

1. A resin composition, comprising:

a hydrocarbon resin containing at least an epoxy-modified hydrocarbon resin;

a crosslinking aid;

the flame retardant at least contains a phosphorus-containing compound (I), and the phosphorus-containing compound (I) is a phosphorus-containing anhydride compound.

2. The resin composition according to claim 1, wherein the epoxy-modified hydrocarbon resin is at least one selected from the group consisting of epoxy-modified polybutadiene, epoxy-modified polypentadiene, epoxy-modified polyisoprene, epoxy-modified styrene-butadiene copolymer, epoxy-modified styrene-butadiene-styrene copolymer, epoxy-modified hydrogenated diene-butadiene-styrene copolymer, and epoxy-modified styrene-pentadiene copolymer.

3. The resin composition of claim 1, wherein the hydrocarbon resin further comprises 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-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, polyisoprene, polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-styrene copolymer, isoprene copolymer, styrene-butadiene, At least one of butadiene-cyclopentadiene copolymer, ethylene-cyclopentadiene copolymer, norbornene polymer, modified norbornene polymer.

4. The resin composition according to claim 1, wherein the hydrocarbon resin is selected from at least one of the following mixtures: a mixture of epoxy-modified polybutadiene and polybutadiene, a mixture of epoxy-modified polypentadiene and polypentadiene, a mixture of epoxy-modified polybutadiene and styrene-butadiene copolymer, and a mixture of epoxy-modified polybutadiene and styrene-butadiene-styrene copolymer.

5. The resin composition according to any one of claims 1 to 4, wherein the phosphorus-containing compound (I) has the following structure:

X₁and X₂Are the same or different, X₁And X₂Are respectively selected from

6. The resin composition according to claim 5, wherein R in the structural formula of the phosphorus-containing compound (I)₃Is a siloxy group selected from

Wherein n is an integer of 1 to 3.

7. The resin composition as claimed in claim 5, wherein the flame retardant further comprises a phosphorus-containing compound (II) selected from phosphazenes, modified phosphazenes, phosphoric acid esters, DOPO-HQ, DOPO-NQ, phosphorus-containing compounds, phosphorus-,

8. The resin composition as claimed in claim 1, wherein the resin composition comprises the following components in percentage by weight: 20-150 parts by weight; crosslinking assistant agent: 1-80 parts by weight; flame retardant: 1-60 parts by weight.

9. The resin composition according to claim 1,

the resin composition includes polybutadiene: 30-70 parts of epoxy modified polybutadiene, 20-70 parts of epoxy modified polybutadiene; TAIC: 2-50 parts by weight; phosphorus-containing compound (I): 1-30 parts by weight; phosphorus-containing compound (II): 1-15 parts.

Or, the resin composition comprises a styrene-butadiene copolymer: 30-60 parts of epoxy modified polybutadiene, 20-70 parts of epoxy modified polybutadiene; triallyl isocyanate monomer: 2-50 parts by weight; phosphorus-containing compound (I): 1-30 parts by weight; phosphorus-containing compound (II): 1-15 parts;

or, the resin composition comprises a styrene-butadiene-styrene copolymer: 30-50 parts of epoxy modified polybutadiene, 20-70 parts of epoxy modified polybutadiene; triallyl isocyanate monomer: 2-50 parts by weight; phosphorus-containing compound (I): 1-30 parts by weight; phosphorus-containing compound (II): 1-15 parts;

or, the resin composition comprises a styrene-butadiene-styrene copolymer: 30-50 parts of epoxy modified polyisoprene, 20-70 parts of epoxy modified polyisoprene; triallyl isocyanate monomer: 2-50 parts by weight; phosphorus-containing compound (I): 1-30 parts by weight; phosphorus-containing compound (II): 1-15 parts.

10. The resin composition of claim 1, wherein the crosslinking coagent 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.

11. A prepreg characterized in that: a resin composition comprising a reinforcing material and impregnated in the reinforcing material, the resin composition being as defined in any one of claims 1 to 10.

12. A laminate, characterized by: comprising at least one prepreg according to claim 11, a metal foil being formed on at least one side of the prepreg.

13. A printed wiring board characterized in that: the printed wiring board comprises at least one prepreg according to claim 11, or at least one laminate according to claim 12.

Technical Field

The invention relates to the technical field of high polymer materials, in particular to a resin composition, and a prepreg, a laminated board and a printed circuit board with the resin composition.

Background

In recent years, with the rapid development of wireless communication technology and electronic products, electronic circuits have come to a stage of high speed information processing and high frequency signal transmission, but when the frequency is higher than 300MHz, even higher than GHz, the electrical properties of the substrate will seriously affect the characteristics of the electronic circuits, and thus the dielectric constant and dielectric loss value of the substrate are required to be higher.

On the other hand, because electronic and electrical equipment have strict requirements on safety and combustion performance, the corresponding printed wiring board for the relevant equipment and prepreg, laminated board and metal foil-clad laminated board also meet the relevant flame-retardant safety requirements. It is conventional practice to use brominated epoxy resins or TBBA or other additive type bromine containing flame retardants. For example, in chinese patent CN101796132B, the flame retardant property is improved by halogen flame retardant to meet the flame retardant requirement. However, such bromine-containing epoxy resins or halogen flame retardants generate harmful substances such as hydrogen halide during combustion, and thus, such flame retardant methods that are harmful to human bodies and the environment have been increasingly focused and controlled. In order to improve the environmental problem, phosphorus-containing flame retardants such as phosphate esters, DOPO, phosphazene or phosphate salts are generally used at present, but it is difficult to select phosphorus-containing flame retardants with good compatibility and reactivity in polyphenylene ether resin systems with poor solubility and compatibility.

Disclosure of Invention

The invention aims to provide a resin composition with low dielectric constant, low dielectric loss, halogen-free flame retardance and high heat resistance, and a prepreg, a laminated board and a printed wiring board prepared by using the resin composition.

In order to achieve the purpose, the invention adopts the following technical scheme:

a resin composition comprising:

a hydrocarbon resin containing at least an epoxy-modified hydrocarbon resin;

a crosslinking aid;

the flame retardant at least contains a phosphorus-containing compound (I), and the phosphorus-containing compound (I) is a phosphorus-containing anhydride compound.

Has the advantages that: according to the resin composition, phosphorus-containing atoms are well introduced into a curing and crosslinking system of the hydrocarbon resin through the reaction of the phosphorus-containing anhydride compound and the epoxy modified hydrocarbon resin, so that the substrate material which simultaneously meets halogen-free flame retardance, low dielectric constant and low dielectric loss value is obtained.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

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 term "comprising" or "containing" in the present specification means that other components capable of imparting different characteristics to the resin composition may be contained in addition to the components.

"based on 100 parts by weight of the resin composition" in the present specification means that the total amount of components excluding the filler, the catalyst, the auxiliary and the initiator is 100 parts by weight.

The resin composition in the preferred embodiment of the present invention comprises (A) a hydrocarbon resin, (B) a crosslinking assistant, and (C) a flame retardant.

Wherein the hydrocarbon resin contains at least an epoxy-modified hydrocarbon resin.

Specifically, the epoxy modified hydrocarbon resin is at least one selected from epoxy modified polybutadiene, epoxy modified polypentadiene, epoxy modified polyisoprene, epoxy modified styrene-butadiene copolymer, epoxy modified styrene-butadiene-styrene copolymer, epoxy modified hydrogenated diene-butadiene-styrene copolymer and epoxy modified styrene-pentadiene copolymer.

Further, the hydrocarbon resin may contain 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, polybutadiene-isoprene copolymer, polybutadiene-butadiene-styrene copolymer, polybutadiene-isoprene copolymer, polybutadiene-, At least one of an ethylene-cyclopentadiene copolymer, a norbornene polymer, and a modified norbornene polymer. "modified" as referred to in this paragraph refers to non-epoxy modifications, that is, modifications of compounds or polymers with any other group than epoxy or epoxy-containing groups, such as hydroxyl, amino or reactive ester group modifications.

In particular, the hydrocarbon resin is selected from at least one of the following mixtures: a mixture of epoxy-modified polybutadiene and polybutadiene, a mixture of epoxy-modified polypentadiene and polypentadiene, a mixture of epoxy-modified polybutadiene and styrene-butadiene copolymer, and a mixture of epoxy-modified polybutadiene and styrene-butadiene-styrene copolymer.

Further preferably, the hydrocarbon resin includes at least one selected from the following structures in addition to the epoxy-modified hydrocarbon resin:

(a is an integer of 1 to 60),

(a is an integer of 1 to 60),

(a and b are the same or different and are respectively selected from integers of 1-60)(a and b are the same or different and are respectively selected from integers of 1-60)

(a, b and c are the same or different and are respectively selected from integers of 1 to 60)

(a is an integer of 1 to 60),

(a is an integer of 1 to 60),

a is an integer of 1 to 60).

Further, in the styrene-butadiene copolymer, the styrene content is 50 mass% or less, and the butadiene content is 50 mass% or more; preferably, the styrene-butadiene copolymer has a styrene content of 20 to 50% by mass, a butadiene content of 50 to 80% by mass, and a 1, 2-ethylene content of 30 to 70% by mass.

The crosslinking assistant is at least one of triallyl isocyanate monomer (TAIC) or prepolymer thereof, butadiene monomer, styrene monomer, pentadiene monomer, norbornene monomer or cyclopentadiene monomer.

Further, the crosslinking aid is preferably TAIC or a prepolymer thereof.

The flame retardant at least contains a phosphorus-containing compound (I), and the phosphorus-containing compound (I) is a phosphorus-containing anhydride compound. Through the reaction of the phosphoric anhydride compound and the epoxy modified hydrocarbon resin, phosphorus-containing atoms are well introduced into a curing crosslinking system of the hydrocarbon resin, and the substrate material which simultaneously meets halogen-free flame retardance, low dielectric constant and low dielectric loss value is obtained.

Specifically, the phosphorus-containing compound (I) has the following structure:

X₁and X₂Are the same or different and are selected from

Wherein R is₁₁And R₁₂Identical or different, R₁₁And R₁₂Are respectively selected from C1-C5 alkyl, benzoxazine, aromatic phenyl, naphthyl, substituted aromatic phenyl or substituted naphthyl; r₁And R₂Identical or different, R₁And R₂Are respectively selected from hydrogen, C1-C5 alkyl, aromatic phenyl, naphthyl, aromatic phenyl containing substituent or naphthyl containing substituent; r₃Selected from hydrogen, C1-C5 alkyl groups or siloxy groups.

Further, X in the structural formula of the phosphorus-containing compound (I)₁And X₂Are all made of

Further, R in the structural formula of the phosphorus-containing compound (I)₁And R₂Are each selected from hydrogen or methyl.

Further, R in the structural formula of the phosphorus-containing compound (I)₃Is hydrogen or a siloxy group selected from

Wherein n is an integer of 1 to 3.

Further, R₃Preferably, it is

When it containsPhosphorus compound formula wherein R₃When the silicon-oxygen radical is selected, the phosphorus radical and the silicon radical are introduced into a hydrocarbon resin system, so that the silicon-oxygen radical has the synergistic flame retardance of phosphorus and silicon, and the heat resistance, weather resistance, flame retardance, dielectric property and low water absorption of the silicon-oxygen radical are well embodied, and therefore the high-frequency high-speed copper-clad plate can provide excellent dielectric property, humidity resistance and heat resistance required by a high-frequency high-speed copper-clad plate.

In any of the above technical solutions of the flame retardant, the flame retardant further contains other phosphorus-containing compound (II), and the phosphorus-containing compound (II) is selected from phosphazenes, modified phosphazenes, phosphate esters, DOPO-HQ, DOPO-NQ, and mixtures thereof,

(m is an integer of 1 to 5),

Or DPO.

The DOPO, DOPO-HQ, DOPO-NQ,

Respectively, the following structures are shown:

preferably, the phosphorus-containing compound (II) is an additive phosphorus-containing compound selected from phosphazenes or modified phosphazenes,

When the phosphorus-containing compound (I) and the phosphorus-containing compound (II) are mixed for use, a phosphorus-containing group is properly introduced into a hydrocarbon resin curing system, and on the basis of satisfying halogen-free flame retardance, the radical curing crosslinking reaction of the hydrocarbon resin is not hindered, so that a substrate material for high frequency and high speed having halogen-free flame retardance, high heat resistance, low dielectric constant and low dielectric loss can be obtained.

When the phosphorus-containing compound (I) and the phosphorus-containing compound (II) are mixed for use, the weight ratio thereof is (1-50): (1-30). For example, the weight ratio of the phosphorus compound (I) to the phosphorus-containing compound (II) is: 50:30.

Any one of the above-mentioned hydrocarbon resin, any one of the above-mentioned crosslinking assistant, and any one of the above-mentioned flame retardant may be combined with each other to constitute the resin composition.

In addition, the resin composition comprises the following components in percentage by weight:

(A) hydrocarbon resin: 20-150 parts by weight;

(B) crosslinking assistant agent: 1-80 parts by weight;

(C) flame retardant: 1-60 parts by weight;

as a further preferred of the present invention, the resin composition comprises, by weight:

(A) polybutadiene: 30-70 parts of epoxy modified polybutadiene, 20-70 parts of epoxy modified polybutadiene;

(B) TAIC: 2-50 parts by weight;

(C) phosphorus-containing compound (I): 1-30 parts by weight; phosphorus-containing compound (II): 1-15 parts;

as a further preferred of the present invention, the resin composition comprises, by weight:

(A) styrene-butadiene copolymer: 30-60 parts by weight of epoxy modified polybutadiene, wherein the weight of the epoxy modified polybutadiene is 20-70 parts by weight;

(B) TAIC: 2-50 parts by weight;

(C) phosphorus-containing compound (I): 1-30 parts by weight; phosphorus-containing compound (II): 1-15 parts;

as a further preferred of the present invention, the resin composition comprises, by weight:

(A) styrene-butadiene-styrene copolymer: 30-50 parts by weight of epoxy modified polybutadiene, wherein the weight of the epoxy modified polybutadiene is 20-70 parts by weight;

(B) TAIC: 2-50 parts by weight;

(C) phosphorus-containing compound (I): 1-30 parts by weight; phosphorus-containing compound (II): 1-15 parts;

as a further preferred of the present invention, the resin composition comprises, by weight:

(A) styrene-butadiene-styrene copolymer: 30-50 parts by weight of epoxy modified polyisoprene, wherein 20-70 parts by weight of epoxy modified polyisoprene;

(B) TAIC: 2-50 parts by weight;

(C) phosphorus-containing compound (I): 1-30 parts by weight; phosphorus-containing compound (II): 1-15 parts;

the resin composition may further include a filler in an amount of 0 to 200 parts by weight based on 100 parts by weight of the resin composition, based on any one of the above resin compositions, and it is understood that the resin composition may or may not include the filler.

For example, the filler content is 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight, 120 parts by weight, 130 parts by weight, 140 parts by weight, 150 parts by weight, 160 parts by weight, 170 parts by weight, 180 parts by weight, 190 parts by weight, or 200 parts by weight; and the particular points between the above numerical values, are not intended to be exhaustive or to be in a concise sense and the invention is not intended to be exhaustive of the particular points included in the range.

Preferably, the filler content is 10 to 100 parts by weight, more preferably 30 to 70 parts by weight.

Specifically, the filler is an organic filler or an inorganic filler, wherein 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; the organic filler is at least one selected from polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder.

More 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.

Preferably, the filler is silica, more preferably, surface-treated spherical silica.

Preferably, the filler has a median particle size 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 not intended to be exhaustive, and for brevity, the invention is not intended to be limited to the specific values included in the ranges.

More preferably, the median value of the particle size of the filler is 1-10 μm.

Specifically, the surface treatment agent for treating the silica is a silane coupling agent such as an epoxy silane coupling agent or an aminosilane coupling agent.

The resin composition may further include a curing accelerator based on any one of the resin compositions described above.

Preferably, the curing accelerator is selected from at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole, and zinc isooctoate, for example: a mixture of 4-dimethylaminopyridine and 2-methylimidazole, a mixture of 2-methylimidazole and 2-methyl-4-ethylimidazole, a mixture of 2-phenylimidazole and zinc isooctoate, and a mixture of 2-methylimidazole, 2-methyl-4-ethylimidazole and 2-phenylimidazole, although not limited thereto.

The curing accelerator is contained in an amount of 0.001 to 5 parts by weight, for example, 0.001 part by weight, 0.01 part by weight, 1 part by weight, 2.5 parts by weight, 5 parts by weight, and specific points between the above-mentioned values, based on 100 parts by weight of the resin composition, are limited to space and in the interest of brevity, and the present invention is not exhaustive of the specific points included in the range.

More preferably, the curing accelerator is contained in an amount of 0.01 to 1 part by weight.

The resin composition may further include an initiator based on any one of the above resin compositions in terms of reactivity between resin components; the initiator is 0.001 to 6 parts by weight based on 100 parts by weight of the resin composition; the initiator can be selected from azo initiators, peroxy initiators and redox initiators, and preferably one or more of the following initiators: dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, cumene hydroperoxide and azobisisobutyronitrile.

Based on any one of the resin compositions, according to different requirements of final products, the resin composition further comprises other auxiliary agents, and preferably, the other auxiliary agents are 0-5 parts by weight based on 100 parts by weight of the resin composition.

The other auxiliary agents comprise at least one of a coupling agent, a dispersing agent and a dye. The coupling agent is a silane coupling agent, such as an epoxy silane coupling agent or an aminosilane coupling agent; the dispersant is amino silane compound having amino group and having hydrolytic group or hydroxyl group such as gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, epoxy silane compound having epoxy group and having hydrolytic group or hydroxyl group such as 3-acryloxypropyltrimethoxysilane, vinyl silane compound having vinyl group and having hydrolytic group or hydroxyl group such as gamma-methacryloxypropyltrimethoxysilane, and cationic silane coupling agent, and the dispersant can be Disperbyk-110, 111, 118, 180, 161, 2009, BYK-W996, W9010, W903 (all product names) manufactured by BYK; the dye is fluorescent dye and black dye, wherein the fluorescent dye is pyrazoline and the like, and the black dye is carbon black (liquid or powder), pyridine complex, azo complex, aniline black, black talcum powder, cobalt chromium metal oxide, azine, phthalocyanine and the like.

The organic solvent and the solvent used in the present invention are not particularly limited. For example, 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 and cyclohexane.

The amount of the solvent to be added is selected by a person skilled in the art according to his own experience, as long as the viscosity of the resulting glue solution is such that it is suitable for use.

The invention also provides a prepreg, which comprises a reinforcing material and the resin composition attached to the surface of the reinforcing material.

The reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric, and the inorganic fabric is preferably glass fiber cloth, and the glass fiber cloth is preferably open fiber cloth or flat cloth.

In addition, when the reinforcing material is a glass cloth, the glass cloth generally needs to be chemically treated to improve the interface between the resin composition and the glass cloth. The main method of the chemical treatment is a coupling agent treatment. The coupling agent used is preferably an epoxy silane, an aminosilane or the like to provide good water resistance and heat resistance.

The preparation method of the prepreg comprises the following steps: and (3) soaking the reinforcing material in the resin composition glue solution, then baking the soaked reinforcing material for 1-10min at the temperature of 50-170 ℃, and drying to obtain the prepreg.

The invention also provides a laminated board which comprises at least one prepreg and the metal foil formed on at least one surface of the prepreg.

The laminated board is formed by bonding one or two prepregs together by heating and pressing, and then bonding a metal foil on one side or two sides of the laminated board by heating and pressing.

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 condition of the laminated board is that the laminated board is pressed for 2-4 hours under the pressure of 0.2-2 MPa and the temperature of 180-250 ℃.

Specifically, the number of prepregs may be determined according to the thickness of a desired laminate, and one or more prepregs may be used.

The metal foil can be copper foil or aluminum foil, and the material is not limited; the thickness of the metal foil is also not particularly limited, and may be, for example, 5 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm.

In order to achieve the above object, the present invention further provides a printed wiring board, which includes at least one prepreg as described above, or at least one laminate as described above.

Compared with the prior art, the invention has the following advantages:

according to the invention, through the reaction of the acid anhydride group in the phosphorus-containing compound and the epoxy group in the hydrocarbon resin, the phosphorus-containing group is well introduced into a hydrocarbon resin curing crosslinking system, and no secondary hydroxyl is generated in the reaction process of the acid anhydride group and the epoxy group, so that the low dielectric constant and low dielectric loss of the hydrocarbon resin are not reduced, and simultaneously, the dielectric constant and dielectric loss value of a cured product are further reduced by matching with other hydrocarbon resins, so that the requirements of the field of the current 5G communication electronic substrate are well met;

when R in the structure of the phosphorus-containing compound (I)₃When the silicon-oxygen base is selected, the phosphorus group and the silicon group are introduced into a hydrocarbon resin system, so that the silicon-oxygen base has the synergistic flame retardance of phosphorus and silicon, and the heat resistance, weather resistance, flame retardance, dielectric property and low water absorption of the silicon-oxygen base are well embodied, and therefore the high-frequency high-speed copper-clad plate can provide excellent dielectric property, humidity resistance and heat resistance required by the high-frequency high-speed copper-clad plate;

when the phosphorus-containing compound (I) and the phosphorus-containing compound (II) are mixed for use, a phosphorus-containing group is properly introduced into a hydrocarbon curing system, the compatibility and reactivity between hydrocarbon resin and other resins are not influenced, and the curing crosslinking reaction of the hydrocarbon resin is not hindered on the basis of meeting halogen-free flame retardance, so that the high-frequency high-speed substrate material with halogen-free flame retardance, high heat resistance, low dielectric constant and low dielectric loss can be obtained.

The following examples are provided to further illustrate embodiments of the present invention. It is to be understood that the embodiments of the present invention are not limited to the following specific examples. The present invention can be modified as appropriate without changing the scope of the claims.

Synthesis example 1: synthesis of phosphorus-containing Compound (I)

Nadic anhydride

And phosphorus compounds

The reaction is carried out in the presence of an initiator benzoyl peroxide, the reaction temperature is 135 ℃, and carbon-carbon double bonds in nadic anhydride are reacted with active hydrogen groups in a phosphorus compound to obtain a phosphorus-containing compound (I) with the following structure A.

Synthesis example 2: synthesis of phosphorus-containing Compound (I)

Mixing internal methyl nadic anhydride

And phosphorus compounds

The reaction is carried out in the presence of an initiator benzoyl peroxide, the reaction temperature is 135 ℃, and carbon-carbon double bonds in nadic anhydride are reacted with active hydrogen groups in a phosphorus compound to obtain a phosphorus-containing compound (I) with the following structure B.

Synthesis example 3: synthesis of phosphorus-containing Compound (I)

Nadic anhydride

And phosphorus compounds

Reacting in the presence of initiator benzoyl peroxide at 135 deg.c to react the carbon-carbon double bond in nadic anhydride with active hydrogen in phosphorus compoundThe following phosphorus-containing compound (I) of structure C is obtained.

Synthesis example 4: synthesis of phosphorus-containing Compound (I)

Mixing silicon-oxygen-containing nadic anhydride

And phosphorus compounds

The reaction is carried out in the presence of an initiator benzoyl peroxide, the reaction temperature is 135 ℃, and carbon-carbon double bonds in nadic anhydride are reacted with active hydrogen groups in a phosphorus compound to obtain a phosphorus-containing compound (I) with the following structure D.