CN104892900A - With bisphenol A-based phosphorus nitrogen epoxy resin, flame retardant composition, composite metal substrate - Google Patents

Abstract

The invention discloses a phosphorus-nitrogen epoxy resin with bisphenol A groups, a flame-retardant composition and a composite metal substrate. The phosphorus-nitrogen epoxy resin is an epoxy resin product obtained by reacting a phosphorus-nitrogen compound having a bisphenol A group with a non-halogen epoxy resin, and the molecular structure of the epoxy resin product contains a bisphenol A group and a group having a phosphorus-nitrogen skeleton composed of unsaturated phosphorus and nitrogen atoms, which are linked to each other, and M contains at least 50 wt% of a group having a cyclic phosphorus-nitrogen skeleton composed of three phosphorus and nitrogen atoms₁) And up to 30 wt% of groups (M) having a chain-like phosphorus-nitrogen skeleton composed of up to two phosphorus and nitrogen atoms₂) And up to 45 wt.% of groups of a cyclic phosphorus-nitrogen skeleton consisting of at least four phosphorus and nitrogen atoms (M)₃) Therefore, the flame retardant has good flame retardance, and a cured product of the flame retardant has good heat resistance, water resistance, cohesiveness, mechanical property and electrical property, so that the flame retardant is an epoxy resin which has greater economy and is environment-friendly.

Description

With bisphenol A-based phosphorus nitrogen epoxy resin, flame retardant composition, composite metal substrate

technical field

The invention relates to the technical field of flame retardant substances, in particular to a bisphenol A-based phosphorus nitrogen epoxy resin, a flame retardant composition, a prepreg, an adhesive sheet, a composite metal substrate and a circuit board.

Background technique

Electronic products represented by mobile phones, computers, cameras, and electronic game consoles, household and office electrical products represented by air conditioners, refrigerators, TV images, audio products, etc., and various products used in other fields, for the sake of safety, a large part All products are required to have different degrees of flame retardancy.

In order to make the product meet the required flame retardant properties or grades, traditional technologies often use inorganic flame retardants such as aluminum hydroxide hydrate, magnesium hydroxide hydrate and other metal hydroxides containing crystal water to the material system. Substances, and adding to the system materials such as brominated bisphenol A, brominated bisphenol A type epoxy resin and other organic chemicals with relatively high bromine content or high halogen content, in order to improve the organic chemistry of these halogens In order to improve the flame retardancy of the material, environmentally unfriendly inorganic chemical flame retardant substances such as antimony trioxide are often added to the system.

Due to the use of halogen-containing flame-retardant substances, non-degradable or refractory toxic substances such as dioxin-like organic halogen chemicals will be produced when burned to pollute the environment and affect human and animal health.

For the purpose of protecting the environment, halogen-free compounds such as phosphorus and nitrogen are used instead of halogen-containing compounds as flame retardants, especially in the electronics, electrical, and electrical industries. Reactive monofunctional (one molecule There is only one active reactive group) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as DOPO), and more derivative compounds of DOPO are used as flame retardant components, adding or Aluminum hydroxide hydrate and magnesium hydroxide hydrate are not added to achieve flame retardant effect.

In the field of electronics, high-cost, multifunctional epoxy resins and DOPO reaction products (referred to as DOPO rings) are usually used Epoxy resin) is widely used as an epoxy resin material for copper clad laminates.

These copper clad laminates made of DOPO epoxy resin have good flame retardant properties, but there are many defects in adhesion, heat resistance, processability, etc., and are not suitable for manufacturing high-layer and high-reliability required by modern communications. , high adhesion, good processing performance, and due to high cost, it is not conducive to the popularization of low-cost consumer electronics such as mobile phones and other civilian products.

With the further improvement of the electronics industry towards short, small, thin, high multi-layer, high reliability requirements, the popularization and use of civilian consumer electronics, and the increasingly severe pressure of environmental pollution, the market urgently needs materials with Flame retardant material with good flame retardancy, heat resistance and good mechanical properties.

Contents of the invention

In view of this, the present invention provides a bisphenol A-based phosphorus nitrogen epoxy resin with good flame retardancy, heat resistance and good mechanical properties.

A bisphenol A-based phosphorus nitrogen epoxy resin, which is an epoxy resin product obtained by reacting a bisphenol A-based phosphorus nitrogen compound and a non-halogen epoxy resin under the condition of excess epoxy resin functional groups;

Wherein the molecular structure of the bisphenol A-based phosphorus nitrogen compound contains bisphenol A groups connected to each other and a group (M) with a phosphorus nitrogen skeleton composed of unsaturated phosphorus and nitrogen atoms, and M contains at least 50wt % of groups (M ₁ ) with ring-shaped phosphorus-nitrogen skeletons composed of three phosphorus and nitrogen atoms, at most 30 wt% of groups with chain-like phosphorus-nitrogen skeletons composed of at most two phosphorus and nitrogen atoms (M ₂ ) and up to 45 wt% of cyclic phosphorus-nitrogen skeleton groups (M ₃ ) composed of at least four phosphorus and nitrogen atoms.

"Excessive epoxy resin functional groups" is based on the fact that the epoxy equivalent of the epoxy resin product is 3585 g/eq or less, more preferably 1520 g/eq or less.

Here, the M group refers to a phosphazene group with a flame-retardant function. M ₁ is a cyclotriphosphazene group; M ₂ specific examples include monophosphazene and bisphosphazene, which can be synthesized by methods commonly used in the art; M ₃ specific examples include cyclotetraphosphazene, cyclopentaphosphazene and cyclopentaphosphazene. Cyclohexaphosphazene, etc. Preferably, M ₁ accounts for more than 80wt% of the total mass of M, particularly preferably, 90-100wt%.

The phosphorus nitrogen compound with bisphenol A group has a molecular structure as shown in formula I:

In formula I, R represents an aliphatic or aromatic group containing at least one carbon atom; a, b, and c are all integers greater than or equal to 1, the sum of b and c is greater than or equal to 2, and any of a, b, and c is The sum is greater than or equal to 6, and n is an integer greater than or equal to zero.

Among the above-mentioned phosphorus nitrogen compounds, if the content of M1 is less _than 50wt%, or if the content of _M2 is more than 30wt%, the product reacted with epoxy resin will damage the necessary properties such as heat resistance, water resistance and mechanical properties during use. . The M ₃ content is at most 45% of the total mass of phosphazene groups. If the content is exceeded, the product reacted with the epoxy resin may cause adverse results such as excessive viscosity, inconvenient use, and damage to its performance due to excessive molecular weight.

The preparation method of the phosphorus nitrogen compound specifically comprises: reacting the above-mentioned chloride compound of M with the compound containing the R group and bisphenol A to obtain the flame retardant. The specific structure and composition of M here are described above in the structure of the flame retardant. The specific reaction adopted can adopt methods known in the art, such as phosphazene chloride compound under the condition of solvent or no solvent, using metal chlorides such as zinc chloride, magnesium chloride, aluminum chloride, boron trifluoride and Its complexes usually use Lewis acid as a catalyst, and react with compounds containing R groups, bisphenol A or its metal salts under basic conditions.

The reaction of the above-mentioned compounds containing R groups, bisphenol A and M chloride can be added to the reaction in one step at the same time, or can be added to the reaction in stages. The object can be.

These catalysts can be used in combination of one or more, and there is no special regulation in the present invention. As for the example of the chloride of M, there is the commonly used hexachlorocyclotriphosphazene, which can be synthesized using known solvents and catalysts, or phosphorus pentachloride and ammonium chloride can be used to synthesize the chlorinated phosphorus cyanide compound according to known methods, Purified by physical methods or directly manufactured without purification.

In the present invention, there is no special regulation on the non-halogen epoxy resin. Here, the "non-halogen epoxy resin" refers to the epoxy resin without halogen atoms, or the epoxy resin with very low halogen content. For example, liquid bisphenol A epoxy resin, liquid bisphenol F epoxy resin, solid bisphenol A epoxy resin, solid bisphenol F epoxy resin, bisphenol S epoxy resin, biphenyl ring Difunctional epoxy resins represented by epoxy resins, such as solid, liquid or semi-solid novolac epoxy resins, o-methyl novolac epoxy resins, bisphenol A novolac epoxy resins, and cycloisoprene epoxy resins Represented by more than three functional epoxy resins. Here, those skilled in the art will easily understand that, of course, when necessary, epoxy resins with relatively low viscosity such as alicyclic epoxy resins, chain aliphatic epoxy resins or ester epoxy resins can also be used, These epoxy resins can be used alone or in combination of two or more, which is not specifically defined in the present invention. Part or most of the above-mentioned epoxy resins can participate in the reaction first, and then add other epoxy resins to participate in the reaction after the reaction reaches a certain degree or complete reaction, or all the necessary epoxy resins can be put into the reaction in stages or at one time. Reaction, the present invention does not make special regulations, to obtain the target object under the premise of ensuring safety and environmental protection.

In order to speed up the reaction speed and save time and energy, it is generally necessary to add a catalyst to the reaction system. The present invention has no special regulations on the type and amount of the catalyst, such as imidazoles, triphenylphosphine and derivatives thereof. General-purpose catalysts for the reaction of epoxy resins and phenolic substances such as amines, tertiary amines, and quaternary ammonium salts can be used. These catalysts can be used alone or in combination of two or more. The amount used is generally within the comparison system The total amount of reacted species is between 100 and 20000 ppm, more usually between 200 and 5000 ppm.

According to the difference of viscosity and other conditions in the reaction system, the method of solvent-free reaction or the method of adding solvent to the reaction system can be adopted. The present invention does not have special regulations on the reaction solvent, such as acetone, methyl ethyl ketone, cyclohexanone Ketone solvents such as benzene, toluene, xylene, mixed xylene and other aromatic solvents, dichloromethane, chloroform, chlorobenzene and other organic chlorine solvents, diethyl ether, butyl ether, ethylene glycol monomethyl ether and other ethers Or ether alcohol solvents, petroleum solvent oil, butanol, isobutanol and other alcohol solvents can be used. These solvents can be used alone or in combination of two or more. The amount of use can be determined according to the actual situation. Depending on the situation, it is generally an amount that enables the solid content of the flame-retardant epoxy resin to be 5-100%, and particularly preferably an amount that enables the solid content of the flame-retardant epoxy resin to be 20-100%.

In order to speed up the reaction speed, it is generally carried out under heating conditions. The reaction temperature is generally in the range of 40-250°C, preferably in the range of 60-180°C. The present invention does not make special regulations to ensure safety and environmental protection. Next, the selection of the target object shall prevail.

Another aspect of the present invention provides a flame retardant composition with good flame retardancy, heat resistance and good mechanical properties.

A flame retardant composition, comprising the above-mentioned epoxy resin with bisphenol A-based phosphorus nitrogen epoxy resin.

The above-mentioned flame retardant composition may only contain flame retardant epoxy resin, and other flame retardant resins or non-flame retardant epoxy resins may be added, such as DOPO type epoxy resin, phosphorus-containing epoxy resin, containing Nitrogen-containing epoxy resin, nitrogen-containing phosphorus-containing epoxy resin, phosphorus-containing phenolic resin, nitrogen-containing phosphorus-containing type phenolic resin, silicon-containing epoxy resin, and sulfur-containing epoxy resin. Of course, curing agents, auxiliary agents, curing accelerators and halogen-free flame-retardant fillers can also be added as needed.

The curing agent is not particularly regulated in the present invention, and substances commonly used as epoxy resin curing agents can be used as the curing agent of the epoxy resin component in the present invention. Specific examples can be amino compounds, such as fatty amines or aromatic amines such as dicyandiamide, diethyltriamine, diaminodiphenylmethane, diaminodiphenylsulfone; it can also be two or more phenolic compounds or Mixtures, such as bisphenol A, bisphenol F, bisphenol S, novolac resin, bisphenol A phenolic resin, etc., contain benzoxazine resin, acid anhydride, polybasic acid, boron trifluoride and its complexes in one molecule etc. These epoxy resin curing agents can be used alone, or two or more of them can be used in combination, and the usage amount is usually between 0.4 and 1.5 (eq) compared to the equivalent ratio of epoxy resins.

For fast curing, it is often necessary to add a curing accelerator. The present invention has no special regulation to the curing accelerator used, and the curing accelerator commonly used in epoxy resin can be used, such as imidazoles, triphenylphosphine and derivatives thereof, tertiary amines, quaternary ammonium salts, The general catalyst for the curing reaction of epoxy resin curing agents such as boron trifluoride and its derivatives can be used. These accelerators can be used alone or in combination of two or more. The amount of use can be determined according to the needs. Subject to safety and environmental protection to obtain the target object, the present invention has no special regulations. Generally, compared with the epoxy resin component in the curing system, 0.001% to 2.5% is more suitable, and the more suitable range is between 0.03% and 1.2%. between.

Fillers are used to increase certain functions, properties or reduce costs. Inorganic fillers such as silica, diatomaceous earth, kaolin, calcium carbonate, mica, titanium dioxide, magnesium hydroxide, aluminum hydroxide, etc. can be added to the curing system. These inorganic fillers can be used alone or in combination of two or more, and the amount used is generally not more than 500 phr of the epoxy resin component (phr means the number of parts contained per 100 grams).

In the above-mentioned flame retardant composition, some general or special substances such as defoamer, coupling agent, toughening agent, leveling agent and the like can be added to the system according to actual needs. There is no special regulation on the amount to be added, and it can be based on the need to obtain the target object in terms of safety and environmental protection.

A prepreg board is formed by impregnating or coating a base material with the above flame retardant composition. The base material can be a glass fiber base material, a polyester base material, a polyimide base material, a ceramic base material or a carbon fiber base material and the like. Here, the specific process conditions of its impregnation or coating are not particularly limited. "Prepreg" is also known to those skilled in the art as "bonded sheet".

A composite metal substrate, which comprises more than one prepreg boards as described above, which are sequentially laminated and laminated with metal-clad layers on the surface. Here, the material of the metal-clad layer on the surface is aluminum, copper, iron and alloys in any combination thereof. Specific examples of composite metal substrates include the following copper-clad laminates, such as CEM-1 copper-clad laminates, CEM-3 copper-clad laminates, FR-4 copper-clad laminates or FR-5 copper-clad laminates, and aluminum substrates.

A circuit board is formed by processing circuits on the surface of the composite metal substrate. The circuit board is widely used in industries such as electronics industry, electrical industry, electrical appliance industry, transportation, aerospace, toy industry, etc. that require circuit boards, such as machines, equipment, instruments, and meters.

The above term "xxx group or group" refers to the remaining part after one or more hydrogen atoms or other atoms or atomic groups are removed from the molecular structure of the xxxx compound.

The bisphenol A-based phosphorus nitrogen epoxy resin of the present invention is an epoxy resin product obtained by reacting a bisphenol A-based phosphorus nitrogen compound and a non-halogen epoxy resin. Phenol A group and a group (M group) with a phosphorus-nitrogen skeleton composed of unsaturated phosphorus and nitrogen atoms, the group with a phosphorus-nitrogen skeleton contains at least 50 wt% of the group consisting of three phosphorus and nitrogen atoms Cyclic phosphorus-nitrogen skeleton group (M ₁ group), up to 30wt% chain-like phosphorus-nitrogen skeleton group ( _M2 group) composed of at most two phosphorus and nitrogen atoms, and up to 45wt% of at least The cyclic phosphorus _- nitrogen skeleton group (M3 group) composed of four phosphorus and nitrogen atoms makes the flame retardant have good flame retardancy, and its cured product has good heat resistance, water resistance, Adhesive and mechanical properties, it is an epoxy resin that is also economical and environmentally friendly.

Detailed ways

The technical solution of the present invention will be further described below in conjunction with the embodiments.

Example 1

Put 86.9g of hexachlorocyclotriphosphorcyanate, 200ml of acetone, 94.0g of phenol, and 250.8g of bisphenol A into a three-port 2000ml glass reactor with a stirring device (while stirring, nitrogen gas flow while heating up to 45°C, use Add 200.0 g of 20% sodium hydroxide solution dropwise for 60 minutes, keep the temperature at 45° C., and stir for 15 hours. After the reaction, remove the moisture in the system by physical methods, then filter to remove the insoluble substances in the system, and distill off the solvent in the system. 374.5 g of flame retardants were obtained, and its phenolic equivalent weight was measured to be 220.1 g/eq, and the target product was named A.

Put 374g of liquid bisphenol A type epoxy resin with an epoxy equivalent of 187g/eq, 125g of the above-mentioned substance A and 0.05g of triphenylphosphine into a three-port 500ml glass reactor with a stirring device, raise the temperature to 100°C, and react 8 Hour, obtain epoxy equivalent and be the object epoxy resin 499.0g of 350.1g/eq, add acetone again and modulate into 60% epoxy resin solution, this object is named after B.

Take 100g of the solution of the above-mentioned substance B (solid content is 60g), add 3.1g of dicyandiamide and an appropriate amount of DMF, stir evenly, add 0.08g of 2-methylimidazole to form a solution, and then follow the general coverage The copper clad laminate production process produces a standard copper clad laminate sample that meets the national standard, UL and other standards, named a copper clad laminate, and tests the performance of the a copper clad laminate. The results are shown in Table-1.

Example 2

Put 180g of dichloroethane, 104.11g of phosphorus pentachloride, 26.75g of ammonium chloride, and 20g of magnesium chloride into a three-port 2000ml glass reactor with a stirring device. Stirring and blowing nitrogen while raising the temperature to 50°C, and reacting at 50°C for 8 hours, then adding 54.02g of sodium methoxide, 94.0g of phenol and 501.6g of bisphenol A, continuing to react for 12 hours, adding solvent 300g, filtered to remove the insoluble matter, and then evaporated the solvent to obtain 689.3g of a flame retardant, whose phenolic equivalent weight was measured to be 203.2g/eq, and the target product was named C.

Put 374g of liquid bisphenol A type epoxy resin with an epoxy equivalent of 187g/eq, 110g of the above-mentioned substance B and 0.05g of triphenylphosphine into a three-port 500ml glass reactor with a stirring device, heat up to 100°C, and react for 10 Hour, obtain epoxy equivalent and be the object epoxy resin 484.0g of 331.2g/eq, this object is named as D.

Take 100g of the solution of the above substance D (solid content is 60g), add 2.85g of dicyandiamide and an appropriate amount of DMF, stir evenly, add 0.08g of 2-methylimidazole to form a solution, and then follow the general coverage Copper plate production procedures produce standard copper clad laminate samples that meet national standards, UL and other standards, named b copper clad laminates, and test the performance of b copper clad laminates. The results are shown in Table-1.

Example 3

Put 173.83g (0.5mol) of hexachlorocyclotriphosphine cyanide, 250ml of acetone, 108.04g of sodium methoxide and 501.6g of bisphenol A into a three-port 2000ml glass reactor with a stirring device, and heat up to 40°C while stirring and nitrogen gas flow. ℃, drop 400g of 20% sodium hydroxide solution over 60min, keep the temperature at 45℃, and stir the reaction for 15 hours. After the reaction, use physical methods to remove the water in the system, then filter to remove the insoluble substances in the system, distill off the solvent in the system, and obtain 667.0g of flame retardants, and the measured phenolic equivalent is 196.2g/eq The object was named E.

Put 374g of liquid bisphenol A type epoxy resin with an epoxy equivalent of 187g/eq, 120g of the above-mentioned substance A and 0.08g of triphenylphosphine into a three-port 500ml glass reactor with a stirring device, raise the temperature to 100°C, and react 8 Hour, obtain epoxy equivalent and be the object epoxy resin 494.0g of 356.2g/eq, add acetone again and modulate into 60% epoxy resin solution, this object is named as F.

Take the solution 100g of the above-mentioned substance F (solid content is 60g), then add 16.7g novolac resin with a phenolic hydroxyl equivalent of 105g/eq and an appropriate amount of acetone, and after the novolac resin is completely dissolved, add 0.08g of 2-methyl Imidazole, made into a solution, and then according to the general copper clad laminate production procedure, a standard copper clad laminate sample that meets the national standard, UL and other standards is prepared, named c copper clad laminate, and the performance of c copper clad laminate is tested. The results are shown in Table-1.

Comparative example 1

Put into the three-port 500ml glass reactor with stirring device and put into epoxy novolak epoxy resin 374g and DOPO 38g and 0.1g triphenylphosphine that the epoxy equivalent is 178g/eq, heat up to 120 ℃, react for 5 hours, get ring Oxygen equivalent is 412g of the object epoxy resin of 232g/eq, this object is named as G.

Take the solution of the above substance G (solid content is 60g), add 3.0g of dicyandiamide and an appropriate amount of DMF, stir evenly, add 0.08g of 2-methylimidazole to make a solution, and then make it according to the general copper clad laminate The program produces standard copper clad laminate samples that meet national standards, UL and other standards, named d copper clad laminates, and tests the performance of d copper clad laminates. The results are shown in Table-1.

Comparative example 2

Get above-mentioned G material solution 100g (solid content 60g), add the novolac resin 27.1g that phenolic hydroxyl equivalent is 105g/eq and the 2-methylimidazole of 0.05g, add appropriate acetone and dissolve after homogeneous solution is made into solution, then according to The general copper clad laminate production procedure produces standard copper clad laminate samples that meet national standards, UL and other standards, named d copper clad laminates, and tests the performance of d copper clad laminates. The results are shown in Table-1.

The test result of embodiment and comparative example is shown in following table-1 (in view of concrete test method is well known to those skilled in the art, method is no longer described in detail at this):

Table-1. Performance comparison of copper clad laminates

The test data in the above table shows that the flame retardant of the present invention and its derivatives have good flame retardancy when used in epoxy resin curing systems and other systems, and their cured products have good heat resistance, water resistance, Bonding and mechanical properties, electrical properties. The flame retardant of the present invention is a new type of environment-friendly and environment-friendly flame retardant material with low cost, abundant raw material sources and good performance in energy saving and emission reduction.

The applicant declares that the present invention illustrates the detailed process equipment and process flow of the present invention through the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, that is, it does not mean that the present invention must rely on the above-mentioned detailed process equipment and process flow process can be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention.

Claims (10)

1. be with a dihydroxyphenyl propane base phosphorus azo-cycle epoxy resins, it is characterized in that, for by band dihydroxyphenyl propane base phosphorus-nitrogen compound and non-halogen system epoxy resin under the condition of epoxy resin functional group surplus, by the epoxy resin resultant be obtained by reacting;

The dihydroxyphenyl propane group be connected with each other and the group (M) being with the phosphorus nitrogen skeleton be made up of unsaturated phosphorus, nitrogen-atoms is comprised, the group (M of the ring-type phosphorus nitrogen skeleton that the band that M comprises at least 50wt% is made up of three phosphorus, nitrogen-atoms in the molecular structure of described band dihydroxyphenyl propane base phosphorus-nitrogen compound ₁), the group (M of chain phosphorus nitrogen skeleton that is made up of two phosphorus, nitrogen-atoms at the most of the band of 30wt% at the most ₂) and the group (M of the ring-type phosphorus nitrogen skeleton be made up of at least four phosphorus, nitrogen-atoms of 45wt% at the most ₃)

Preferably, the epoxy equivalent (weight) of described non-halogen system epoxy resin is at below 3585g/eq; More preferably at below 1520g/eq.

2. band dihydroxyphenyl propane base phosphorus azo-cycle epoxy resins according to claim 1, it is characterized in that, described band dihydroxyphenyl propane base phosphorus-nitrogen compound has such as formula the molecular structure shown in I:

In formula I, R represents aliphatic group containing at least one carbon atom or aromatic base; A, b, c are the integer being more than or equal to 1, b and c sum is more than or equal to 2, a, b and c three sum be more than or equal to 6, n be more than or equal to zero integer.

Preferably, M ₁account for more than the 80wt% of M total mass, more preferably 90 ~ 100wt%.

3. band dihydroxyphenyl propane base phosphorus azo-cycle epoxy resins according to claim 1, is characterized in that, described reaction catalyst-free or have catalyzer condition under carry out;

Preferably, described catalyzer is imidazoles, triphenylphosphine and derivatives class thereof, one in tertiary amines and quaternary ammonium salts catalyzer is used alone or multiple used in combination;

Preferably, the consumption of described catalyzer is relative to band dihydroxyphenyl propane base phosphorus-nitrogen compound 0.01 ~ 2.5%, is more preferably 0.02% ~ 0.5%;

Preferably, the temperature of described reaction is 40 ~ 250 DEG C, more preferably 60 ~ 180 DEG C.

4. band dihydroxyphenyl propane base phosphorus azo-cycle epoxy resins according to claim 1, it is characterized in that, described reaction is carried out under condition that is solvent-free or that have solvent, and described solvent is one in ketones solvent, aromatic solvents, chlorinated solvents, ether solvent, ether alcohol kind solvent, alcoholic solvent and petroleum solvent oil or at least two kinds;

Preferably, the consumption of described solvent is to make band dihydroxyphenyl propane base phosphorus azo-cycle epoxy resins solid content be the consumption of 5 ~ 100%, and band dihydroxyphenyl propane base phosphorus azo-cycle epoxy resins solid content more preferably can be made to be the consumption of 20 ~ 100%.

5. band dihydroxyphenyl propane base phosphorus azo-cycle epoxy resins according to claim 1, is characterized in that, described non-halogen system epoxy resin is epoxy resin more than two senses or two senses;

Preferably, the epoxy resin of two senses is one in liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, solid-state bisphenol A type epoxy resin, solid-state bisphenol f type epoxy resin and bisphenol-s epoxy resin, biphenyl type epoxy resin or at least two kinds;

Preferably, the epoxy resin more than two senses is the one of phenol aldehyde type epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin and acyclic isoprenoid type epoxy resin or at least two kinds.

6. a fire-retardant combination, is characterized in that, comprises band dihydroxyphenyl propane base phosphorus azo-cycle epoxy resins as claimed in claim 1.

7. fire-retardant combination according to claim 6, is characterized in that, also comprises the filler of epoxy fat resin, solidifying agent, auxiliary agent, curing catalyst and the halogen-free flame-retardance with flame retardant resistance;

Preferably, the resin described in flame retardant resistance is DOPO type epoxy resin, containing phosphorous epoxy resin, nitrogenous type epoxy resin, nitrogenous containing phosphorous epoxy resin, phosphorus-containing phenolic aldehyde epoxy resin, nitrogenous containing the one in phosphorous novolac epoxy, silicon-contained type epoxy resin and sulfur-type epoxy resin or at least two kinds;

Preferably, described solidifying agent is one in polyphenol based compound, amino-complex, benzoxazine colophony, acid anhydrides, polyprotonic acid and boron trifluoride and complex compound thereof or at least two kinds;

Preferably, described amino-complex is aliphatic amide or the aromatic amines such as Dyhard RU 100, diethyl triamine, diaminodiphenylmethane, diaminodiphenylsulfone(DDS);

Preferably, described polyphenol based compound is one in dihydroxyphenyl propane, Bisphenol F, bisphenol S, linear phenolic resin, o-cresol urea formaldehyde, bisphenol A phenolic resin or at least two kinds;

Preferably, the consumption of described solidifying agent and the equivalence ratio 0.4 ~ 1.5 of epoxy resin;

Preferably, described curing catalyst is one in imidazoles, triphenylphosphine and derivatives class thereof, tertiary amines, quaternary ammonium salts and boron trifluoride and derivatives class thereof or at least two kinds;

Preferably, the consumption of described curing catalyst is account for epoxy resin total mass 0.001 ~ 2.5%, more preferably 0.03 ~ 1.2%;

Preferably, described filler is one in silicon-dioxide, kaolin, calcium carbonate, mica, titanium dioxide, magnesium hydroxide, aluminium hydroxide or at least two kinds;

Preferably, the consumption of described filler is below the 500phr of epoxy resin total mass;

Preferably, described auxiliary agent is one or more in defoamer, coupling agent, toughner and flow agent.

8. a pre-impregnated sheet, is characterized in that, it is by fire-retardant combination impregnation as claimed in claim 7 or coat base material and form;

Preferably, described base material is fiberglass substrate, polyester base material, polyimide base material, ceramic base material or carbon fiber base material.

9. a composite metal substrate, is characterized in that, it comprises more than one, and pre-impregnated sheet carries out surperficial metal-clad successively as claimed in claim 8, overlap, pressing form;

Preferably, the material of described surperficial metal-clad is the alloy of aluminium, copper, iron and arbitrary combination thereof;

Preferably, described composite metal substrate is but is not limited to CEM-1 copper-clad plate, CEM-3 copper-clad plate, FR-4 copper-clad plate, FR-5 copper-clad plate, CEM-1 aluminium base, CEM-3 aluminium base, FR-4 aluminium base or FR-5 aluminium base.

10. a wiring board, is characterized in that, the surface working circuit in composite metal substrate according to claim 9 forms.