CN1249128C - Flame Retardant Resin Composition - Google Patents

Abstract

The present invention relates to a phosphorus-containing resin and a flame-retardant resin composition containing the same. The flame-retardant resin composition comprises the phosphorus-containing resin, a nitrogen-containing resin curing agent and a curing reaction accelerator. The flame retardant resin composition is halogen-free and has good flame retardant properties and high heat resistance without adding a flame retardant, and can be used for manufacturing adhesive sheets, composite materials, laminated plates, printed circuit boards, copper foil adhesives and semiconductor sealing materials.

Description

Flame Retardant Resin Composition

The invention relates to a phosphorus-containing resin and a flame-retardant resin composition containing the resin.

Composite materials, especially epoxy resin composite materials, are widely used in painting, electrical insulation, civil engineering materials, adhesives and In various fields such as laminated products. Among them, the laminated board made of epoxy resin has strong adhesion to reinforcing materials such as glass fiber cloth, does not produce volatile matter during curing, and has small molding shrinkage. Therefore, the obtained laminated board has a wide range of applications. The advantages of excellent mechanical strength, good electrical insulation, and good chemical resistance greatly improve the reliability of laminated sheets, making epoxy laminated sheets widely used in electrical and electronic products.

However, in order to meet the increasingly precise and high-density requirements of printed circuit boards, laminates are also required to have more excellent electrical properties, mechanical properties and thermal processing resistance. Taking the current common FR4 laminates as an example, the glass transition temperature after curing is mostly around 130°C. For the cutting and drilling processing of more than 200°C in the printed circuit board manufacturing process, and even the welding process above 270°C, such Laminate materials have the potential to crack or burst during manufacturing and processing. Therefore, people are actively developing various laminate materials with high thermal stability and high glass transition temperature. In addition, another important property for laminates is their flame retardant properties. In some occasions, such as airplanes, automobiles and public transportation, etc., because it directly threatens the safety of human body and life, the flame retardant characteristics of printed circuit boards are absolutely necessary.

In order to introduce flame retardant properties into laminate materials, it is necessary to use certain substances that have flame-isolated flame-reducing properties. For epoxy resin/glass fiber (or organic fiber) laminates, halogen-containing compounds, especially bromine-containing epoxy resins and curing agents, and flame retardant additives such as antimony trioxide, In order to meet the stringent requirements for the flame retardant properties of laminates (such as UL 94V-0 grade). Usually, epoxy resin needs to contain as high as 17% to 21% bromine content, and use antimony trioxide or other flame retardants together to reach the level of UL 94V-0. However, the use of high bromine content epoxy resin or antimony trioxide will undoubtedly bring some dangers to human beings.

First of all, antimony trioxide has been listed as a carcinogen; on the other hand, bromine not only produces corrosive bromine free radicals and hydrogen bromide during combustion, but also aromatic compounds with high bromine content will produce highly toxic Brominated furans and brominated dioxins (dioxins) have seriously affected human health and the environment. Therefore, it is urgent to seek a new flame-retardant material and flame-retardant method to improve the pollution and environmental protection problems caused by the use of brominated epoxy resin in the current laminate. In particular, the demand for FR-4 epoxy-glass fiber laminates is greater as the usage is large.

Phosphorus compounds, as a new generation of environmentally friendly flame retardants, have been widely studied and applied. For example, direct use of red phosphorus or phosphorus organic compounds (such as triphenylphosphonate, tritylphosphonate, carbonic acid, etc.) to replace halogen compounds as flame retardants to improve polymer materials or curable resins combustion characteristics. However, directly adding these compounds to the resin not only requires a large amount of addition due to the limitation of the flame retardant efficiency of these compounds, but also because of its low molecular weight and high mobility will directly affect the characteristics of the resin substrate: such as Electrical properties, adhesive strength, etc., cause practical difficulties.

In recent years, with the concept of reactive flame retardants and environmental protection and safety considerations, phosphating epoxy resins have been used to replace brominated epoxy resins as the formulation of flame-retardant laminates, such as US Patent No. 5,376,453, using belt rings Oxygen-based phosphates are combined with nitrogen-containing cyclic curing agents to make laminates, but in order to make up for the shortcomings of insufficient phosphorus content that is difficult to meet the requirements of UL 94V-0, a variety of phosphate epoxides are added; US Patent No. 5458978 Using epoxy phosphate ester combined with nitrogen-containing epoxy resin and metal compound as a curing agent, the glass transition temperature of the finished product is about 175°C, and the flame retardancy reaches the edge of UL 94V-0 (42 seconds relative to the critical value of 50 seconds) ). U.S. Patent No. 4973631 and U.S. Patent No. 5086156 use trihydrocarbyl phosphine chloride alone or in conjunction with other amine curing agents with active hydrogen substituents (such as amino groups) for the curing of epoxy resins; yet the curing agent is introduced into phosphorus for The resin has the disadvantage of low phosphorus content, and there is no measurement of the actual flame retardant effect in the two patents.

The present invention aims at improving the basic properties of electrical and mechanical properties and reducing costs, aiming at the above-mentioned shortcomings in the prior art, thus completing the present invention.

An object of the present invention is to provide a kind of phosphorus-containing resin, and the flame-retardant resin composition based on this phosphorus-containing resin has excellent flame retardancy, electrical properties and mechanical properties;

Another object of the present invention is to provide a flame-retardant resin composition of the phosphorus-containing resin.

A kind of phosphorus-containing resin of the present invention, the characteristic of this phosphorus-containing resin is to contain the functional group of following formula (A):

The functional group represented by the formula (A) in the phosphorus-containing resin of the present invention is composed of the epoxy group of the epoxy resin and 9,10-dihydro-9-oxa-10-phosphoranthracene- The 10-oxide reacts to give:

The phosphorus-containing resin of the present invention can be prepared by reacting known epoxy resins with 9,10-dihydro-9-oxa-10-phosphoranthracene-10-oxide and other active hydrogen-containing compounds as the case may be .

The epoxy resin for manufacturing the phosphorus-containing resin of the present invention can be any epoxy resin, and its specific examples include bisphenol glycidyl ether, bisbiphenol glycidyl ether, hydroquinone glycidyl ether, glycidyl ether of nitrogen-containing ring, Glycidyl ether of dihydroxynaphthalene, phenolic polyglycidyl ether and polyhydric phenol polyglycidyl ether, etc.

Bisphenol glycidyl ethers include, for example, bisphenol A glycidyl ether, bisphenol F glycidyl ether, bisphenol AD glycidyl ether, bisphenol S glycidyl ether, tetramethylbisphenol A glycidyl ether, tetramethylbisphenol F glycidyl ether, tetramethyl bisphenol AD glycidyl ether, tetramethyl bisphenol S glycidyl ether.

Bisdiphenol glycidyl ethers include, for example, 4,4'-diphenol glycidyl ether, 3,3'-dimethyl-4,4'-diphenol glycidyl ether, 3,3',5,5'-tetra Methyl-4,4'-diphenol glycidyl ether.

Hydroquinone glycidyl ether includes, for example, resorcinol glycidyl ether, hydroquinone glycidyl ether, and isobutylhydroquinone glycidyl ether.

The phenolic polyglycidyl ether includes, for example, phenolic polyglycidyl ether, cresol novolac polyglycidyl ether, bisphenol A novolac polyglycidyl ether.

Polyhydric phenol polyglycidyl ethers include, for example, tris(4-hydroxyphenyl)methane polyglycidyl ether, tris(4-hydroxyphenyl)ethane polyglycidyl ether, tris(4-hydroxyphenyl)propane polyglycidyl ether ether, tris(4-hydroxyphenyl)butane polyglycidyl ether, tris(3-methyl-4-hydroxyphenyl)methane polyglycidyl ether, tris(3,5-dimethyl-4-hydroxybenzene base) methane polyglycidyl ether, tetrakis (4-hydroxyphenyl) ethane polyglycidyl ether, tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane polyglycidyl ether, dicyclopentene- Phenolic polyglycidyl ether.

Glycidyl ethers of nitrogen-containing rings include, for example, triglycidyl ethers of isocyanurates and triglycidyl ethers of cyanurates.

Glycidyl ethers of dihydroxynaphthalene include, for example, 1,6-dihydroxynaphthalene diglycidyl ether and 2,6-dihydroxynaphthalene diglycidyl ether.

The epoxy resins mentioned above can be used alone or in combination of two or more.

Wherein it is preferably bisphenol A polyglycidyl ether, phenolic polyglycidyl ether, three (4-hydroxyphenyl) methane polyglycidyl ether, dicyclopentene-phenolic polyglycidyl ether and four (phenyl) of four functional groups -4-hydroxy)ethane polyglycidyl ether, or a mixture thereof.

Other optional active hydrogen-containing compounds for producing the phosphorus-containing resin of the present invention include amines, bisphenol resins, quinone, polyhydric phenol resins, phenolic resins, and the like.

Amines include, for example, dicyandiamide, diaminodiphenylmethane.

Bisphenol resins comprise, for example, the formula HO-Ph-X-Ph-OH (where Ph represents phenyl, X = -CH ₂ -C(CH ₃ ) ₂ -, -O-, -S-, -CO-, -SO ₂ -) Compounds represented, for example: bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol Bisphenol S, 4,4'diphenol, 3,3'-dimethyl-4,4'diphenol, 3,3',5,5'-tetramethyl-4,4'diphenol.

Hydroquinone includes, for example, resorcinol, hydroquinone, isobutylhydroquinone.

Polyhydric phenol resins include, for example, tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane, tris(4-hydroxyphenyl)butane, 3-methyl-4-hydroxyphenyl)methane, tris(3,5-dimethyl-4-hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethane, tetrakis(3,5-dimethyl -4-hydroxyphenyl)ethane.

Suitable phenolics are, for example: phenol-formaldehyde condensates, cresol-phenol-formaldehyde condensates, bisphenol A-phenol-formaldehyde condensates, dicyclopentene-phenol-formaldehyde condensates.

In the phosphorus-containing resin of the present invention, the use ratio of the above-mentioned components is epoxy resin epoxy equivalent: formula (B) compound active hydrogen equivalent: other active hydrogen-containing compound active hydrogen equivalent=100: (5～50): (0-45), preferably 100:(10-50):(0-45), more preferably 100:(15-40):(0-45). If the content of the compound of formula (B) is too high, the viscosity of the resin solution will increase, and if the content of the compound of formula (B) is too low, the flame retardancy of the cured product will deteriorate. Excessive content of other active hydrogen-containing compounds will cause the molecular weight of the resin to be too large, and even cause the phosphorus-containing epoxy resin to cure and become unusable.

In the production of the phosphorus-containing resin of the present invention, in addition to the above-mentioned components, a catalyst may be added to facilitate the reaction. The catalyst used includes tertiary amine, tertiary phosphine, quaternary ammonium salt, quaternary phosphonium salt, boron trifluoride complex, lithium compound, imidazole compound and mixture thereof.

Tertiary amines such as triethylamine, tributylamine, dimethylamine ethanol, dimethylphenylamine, tris(N,N-dimethyl-aminomethyl)phenol, N,N-dimethyl - Aminomethylphenol.

Tertiary phosphine such as triphenylphosphine.

Quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, triethylbenzyl ammonium chloride, triethylbenzyl ammonium bromide, triethylbenzyl ammonium ammonium iodide.

Quaternary phosphonium salts such as tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, tetrabutylphosphonium acetate complex, tetraphenylphosphonium chloride, tetraphenylphosphonium Phosphonium Bromide, Tetraphenylphosphonium Iodide, Ethyltriphenylphosphonium Chloride, Ethyltriphenylphosphonium Bromide, Ethyltriphenylphosphonium Iodide, Ethyltriphenylphosphonium Ester Acid Complex Phosphate, Ethyltriphenylphosphonium Ester Phosphate Complex, Propyltriphenylphosphonium Chloride, Propyltriphenylphosphonium Bromide, Propyltriphenylphosphonium Iodide, Butyltriphenylphosphonium Chloride , Butyltriphenylphosphonium bromide, Butyltriphenylphosphonium iodide, etc.

Examples of imidazole compounds include 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole and the like.

The catalysts mentioned above can be used alone or in combination of two or more.

Preferred catalysts are tertiary amines and imidazole compounds, especially dimethylaniline, 2-methylimidazole, 2-phenylimidazole and 2-ethyl-4-methylimidazole.

The catalyst is used in an amount of 50-50,000 ppm, preferably 100-30,000 ppm, more preferably 200-10,000 ppm, still more preferably 500-2,000 ppm, based on the total weight of the starting material. If the amount of catalyst exceeds 50,000ppm, although the reaction time can be shortened, it will have adverse effects on the formation of by-products and subsequent applications such as electrical properties, moisture resistance, and water absorption properties of circuit board laminates. If the amount added is too small, then The reaction rate is too slow to be efficient.

The reaction for preparing the phosphorus-containing resin of the present invention can be carried out by melt addition reaction in the absence of a solvent, or by reflux reaction in the presence of a solvent.

Suitable solvents for use include organic aromatics, ketones, protic solvents, ethers, esters, and the like.

Suitable organic aromatics are eg: toluene, xylene.

Suitable ketones are, for example: acetone, methyl ethyl ketone, methyl isobutyl ketone.

Suitable protic solvents are, for example: N,N-dimethylformamide, N,N-diethylformamide, dimethylsulfoxide.

Suitable ethers are, for example: ethylene glycol monomethyl ether, propylene glycol monomethyl ether.

Suitable esters are, for example: ethyl acetate, ethyl isopropionate, ethyl propylene glycol monomethyl ether.

The reaction temperature for preparing the phosphorus-containing resin of the present invention is generally 50-350°C, preferably 50-300°C, more preferably 100-250°C, and most preferably 100-200°C. If the temperature is too high, side reactions will easily occur, making it difficult to control the reaction rate, and will accelerate the deterioration of the resin; if the temperature is too low, in addition to poor efficiency, the resulting resin characteristics are difficult to meet the needs of high temperature use.

The present invention also relates to a flame-retardant resin composition, which includes (a) the phosphorus-containing resin of the present invention, (b) a curing agent represented by the following formula (C), and (c) a curing accelerator.

In the formula, R ² represents -[CH ₂ -R ³ ] _n H (n is an integer from 0 to 20) or a hydrogen atom; but at least one R ² is not a hydrogen atom:

R ¹ represents NHR ² , C _1-6 alkyl or phenyl,

R ³ represents phenylene, naphthylene or a group with the following formula structure:

In the formula, A represents -O-, -S-, -SO ₂ -, -CO-, -CH ₂ -, -C(CH ₃ ) ₂ - or a group with the following structure:

或

or

Among the groups represented by ^R3 and A above, the aromatic group may be substituted by one or more substituents selected from hydroxyl, amino, carboxyl, and _C1-6 alkyl.

The curing accelerator in the flame retardant resin composition of the present invention includes tertiary amine, tertiary phosphine, quaternary ammonium salt, quaternary phosphonium salt, boron trifluoride complex, lithium compound, imidazole compound and mixtures thereof.

Tertiary amines such as triethylamine, tributylamine, dimethylamine ethanol, dimethylphenylamine, tris(N,N-dimethyl-aminomethyl)phenol, N,N-dimethyl - Aminomethylphenol.

Tertiary phosphine such as triphenylphosphine.

Quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, triethylbenzyl ammonium chloride, triethylbenzyl ammonium bromide, triethylbenzyl ammonium ammonium iodide.

Quaternary phosphonium salts such as tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, tetrabutylphosphonium ester salt acetate complex, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, Tetraphenylphosphonium iodide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium ester salt acetate complex, ethyl triphenylphosphonium Phenylphosphonium ester phosphate complex, propyltriphenylphosphonium chloride, propyltriphenylphosphonium bromide, propyltriphenylphosphonium iodide, butyltriphenylphosphonium chloride, butyltriphenyl Phosphonium bromide, butyltriphenylphosphonium iodide, etc.

Examples of imidazole compounds include 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole and the like.

The curing accelerators mentioned above may be used alone or in combination of two or more.

Preferred curing accelerators are tertiary amines and imidazole compounds, especially dimethylaniline, 2-methylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole.

The amount of the curing accelerator used is 50-50,000 ppm, preferably 100-30,000 ppm, more preferably 200-10,000 ppm, most preferably 500-2,000 ppm, based on the total weight of the flame retardant resin composition. If the amount of curing accelerator exceeds 50,000ppm, although the reaction time can be shortened, it will adversely affect the generation of by-products and the electrical properties, moisture resistance, and water absorption properties of subsequent applications such as circuit board laminates. If the amount added is too large Small, the reaction rate is too slow to be efficient.

The flame-retardant resin composition of the present invention may contain other phosphorus-free epoxy resins in addition to the phosphorus-containing resin of the present invention.

The phosphorus-free epoxy resin may be any epoxy resin, and specific examples thereof include bisphenol glycidyl ether, bisbiphenol glycidyl ether, hydroquinone glycidyl ether, nitrogen-containing ring glycidyl ether, dihydroxynaphthalene Glycidyl ether, phenolic polyglycidyl ether and polyhydric phenol polyglycidyl ether, etc.

Bisphenol glycidyl ethers include, for example, bisphenol A glycidyl ether, bisphenol F glycidyl ether, bisphenol AD glycidyl ether, bisphenol S glycidyl ether, tetramethylbisphenol A glycidyl ether, tetramethylbisphenol F glycidyl ether, tetramethyl bisphenol AD glycidyl ether, tetramethyl bisphenol S glycidyl ether.

Bisdiphenol glycidyl ethers include, for example, 4,4'-diphenol glycidyl ether, 3,3'-dimethyl-4,4'-diphenol glycidyl ether, 3,3',5,5'-tetra Methyl-4,4'-diphenol glycidyl ether.

Hydroquinone glycidyl ether includes, for example, resorcinol glycidyl ether, hydroquinone glycidyl ether, and isobutylhydroquinone glycidyl ether.

The phenolic polyglycidyl ether includes, for example, phenolic polyglycidyl ether, cresol novolac polyglycidyl ether, bisphenol A novolac polyglycidyl ether.

Polyhydric phenol polyglycidyl ethers include, for example, tris(4-hydroxyphenyl)methane polyglycidyl ether, tris(4-hydroxyphenyl)ethane polyglycidyl ether, tris(4-hydroxyphenyl)propane polyglycidyl ether ether, tris(4-hydroxyphenyl)butane polyglycidyl ether, tris(3-methyl-4-hydroxyphenyl)methane polyglycidyl ether, tris(3,5-dimethyl-4-hydroxybenzene base) methane polyglycidyl ether, tetrakis (4-hydroxyphenyl) ethane polyglycidyl ether, tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane polyglycidyl ether, dicyclopentene- Phenolic polyglycidyl ether.

Glycidyl ethers of nitrogen-containing rings include, for example, triglycidyl ethers of isocyanurates and triglycidyl ethers of cyanurates.

Glycidyl ethers of dihydroxynaphthalene include, for example, 1,6-dihydroxynaphthalene diglycidyl ether and 2,6-dihydroxynaphthalene diglycidyl ether.

In the flame retardant resin composition of the present invention, one or more of the above-mentioned phosphorus-free epoxy resins can be used in combination or a mixture of two or more of the above-mentioned phosphorus-free epoxy resins can be used in combination. Wherein it is preferably bisphenol A polyglycidyl ether, phenolic polyglycidyl ether, three (4-hydroxyphenyl) methane polyglycidyl ether, dicyclopentene-phenolic polyglycidyl ether and four (phenyl) of four functional groups -4-hydroxy)ethane polyglycidyl ether, or a mixture thereof.

When the phosphorus-free epoxy resin is used in combination, the proportion of the phosphorus-containing resin of the present invention accounts for 5-100% of the total weight of the epoxy resin, preferably 20-100%, more preferably 25-100%. If the ratio is too low, the flame retardancy and heat resistance will be insufficient.

In addition to the aforementioned compound of formula (C), the flame retardant resin composition of the present invention may also contain other curing agents, such as amines, bisphenol resins, diphenols, polyhydric phenol resins, and phenolic resins.

Amines include, for example, dicyandiamide, diaminodiphenylmethane.

Bisphenol resins comprise, for example, the formula HO-Ph-X-Ph-OH (where Ph represents phenyl, X = -CH ₂ -C(CH ₃ ) ₂ -, -O-, -S-, -CO-, -SO ₂ -) Compounds represented, for example: bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol Bisphenol S, 4,4'diphenol, 3,3'-dimethyl-4,4'diphenol, 3,3',5,5'-tetramethyl-4,4'diphenol.

Hydroquinone includes, for example, resorcinol, hydroquinone, isobutylhydroquinone.

Polyhydric phenol resins include, for example, tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane, tris(4-hydroxyphenyl)butane, 3-methyl-4-hydroxyphenyl)methane, tris(3,5-dimethyl-4-hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethane, tetrakis(3,5-dimethyl -4-hydroxyphenyl)ethane.

Suitable phenolics are, for example: phenol-formaldehyde condensates, cresol-phenol-formaldehyde condensates, bisphenol A-phenol-formaldehyde condensates, dicyclopentene-phenol-formaldehyde condensates.

In the example of using other curing agents, the proportion of the curing agent of the compound of formula (C) is 5-100% of the total weight of the curing agent, preferably 20-100%, most preferably 25-100%. If the ratio is too low, the flame retardancy and heat resistance will be insufficient.

In the flame retardant resin composition of the present invention, the amount of curing agent added depends on the reactive hydrogen equivalent of each curing agent and the epoxy equivalent of the epoxy resin, and the suitable equivalent ratio is 100% to the epoxy equivalent of the epoxy resin Calculated, the reactive hydrogen equivalent of the curing agent is 20 to 140%, the preferred equivalent ratio is 100% of the epoxy equivalent of the epoxy resin, the reactive hydrogen equivalent of the curing agent is 40 to 95%, the more preferred equivalent ratio Based on 100% of the epoxy equivalent of the epoxy resin, the reactive hydrogen equivalent of the curing agent is 50-95%.

When preparing the flame retardant resin composition of the present invention as a varnish, a solvent may be added to adjust the viscosity. Suitable solvents include organic aromatics, ketones, protic solvents, ethers, esters, and the like.

Suitable organic aromatics are eg: toluene, xylene.

Suitable ketones are, for example: acetone, methyl ethyl ketone, methyl isobutyl ketone.

Suitable protic solvents are, for example: N,N-dimethylformamide, N,N-diethylformamide, dimethylsulfoxide.

Suitable ethers are, for example: ethylene glycol monomethyl ether, propylene glycol monomethyl ether.

Suitable esters are, for example: ethyl acetate, ethyl isopropionate, ethyl propylene glycol monomethyl ether.

The viscosity is usually adjusted to 20 to 500 cps/25°C.

Depending on the end use, general additives or modifiers, such as heat stabilizers, light stabilizers, ultraviolet light absorbers and plasticizers, can also be added to the flame retardant resin composition of the present invention.

The flame retardant resin composition of the present invention can be made into a laminate together with platinum foil and fiber support using methods known in the general industry.

Use the flame retardant resin composition of the present invention to prepare a varnish (varnish), impregnate a fiber substrate such as an organic or inorganic fiber substrate (such as glass fiber, metal fiber, carbon fiber, aramid fiber, boron and cellulose, etc.) with the varnish, The impregnated fibrous substrate is heated and dried to obtain a dry prepreg. The prepreg can be further molded into a composite material laminate, or the prepreg can be used alone as an adhesive layer for other films, or one or more prepregs can be combined, on the upper side or Copper foil is placed on the upper and lower sides, and the prepreg or its composition is heated under pressure to obtain a laminated board composite material. The obtained laminated board composite material has excellent dimensional stability, chemical resistance, corrosion resistance, moisture absorption Both its electrical and electrical properties have exceeded the current product standards, and are suitable for the manufacture of electrical products used in electronics, space, transportation, etc., such as printed circuit boards and multilayer circuit boards.

The flame-retardant resin composition of the present invention can also be formulated into a varnish, coated on copper foil, and heated and dried to obtain a dry resin-coated copper foil (RCC, Resin Coated Copper). The resin-coated copper foil can be stored for several months at room temperature and has good storage stability. The resin-coated copper foil can be further formed into a composite laminate, or used alone as an adhesive layer for other films, or one or more of the resin-coated copper foils can be combined on it One side or the upper and lower sides are laminated layer by layer (build-up) to obtain a laminate composite material. The obtained laminate composite material has excellent dimensional stability, chemical resistance, corrosion resistance, and moisture absorption. Both electrical and electrical properties have exceeded the current product standards, and are suitable for the manufacture of multilayer printed circuit boards used in electronics, space, transportation, etc.

The suitable curing reaction temperature of the flame retardant resin composition of the present invention is 20-350°C, preferably 50-300°C, more preferably 100-250°C, still more preferably 120-220°C. If the temperature is too high, side reactions are likely to occur, and it is difficult to control the reaction speed, and may accelerate the deterioration of the resin; if the temperature is too low, in addition to poor efficiency, the properties of the resin produced are difficult to meet the requirements of high temperature use.

The flame retardant resin composition formed according to the present invention does not need to add other processing aids and flame retardant additives, and can simultaneously improve the flame retardancy and heat resistance of the epoxy resin.

The present invention will be further illustrated with the following synthesis examples and examples, but the scope of the present invention is not limited thereby.

Each component used in the synthesis example and the embodiment is described in detail as follows:

Epoxy resin 1 is produced by Changchun Artificial Resin Factory, the polyglycidyl ether of the cresol-phenolic condensate sold under the trade name CNE200ELB, and its epoxy equivalent is 200～220g/eq, and hydrolyzable chlorine is below 700ppm (ASTM method ).

Epoxy resin 2 is a phenolic polyglycidyl ether produced by Changchun Artificial Resin Factory and sold under the trade name PNE177. Its epoxy equivalent is 170-190g/eq, and its hydrolyzable chlorine is less than 1000ppm (ASTM method).

Epoxy resin 3 is a diglycidyl ether of bisphenol A produced by Changchun Artificial Resin Factory and sold under the trade name BE188EL. The epoxy equivalent is 185-195g/eq, the hydrolyzable chlorine is below 200ppm, and the viscosity is 11000-15000cps /25°C.

Epoxy resin 4 is produced by Changchun Artificial Resin Factory, the trade name is BE501, and its epoxy equivalent is 490～510g/eq.

Epoxy resin 5 is produced by Changchun Artificial Resin Factory and sold under the trade name BEB530A80 as diglycidyl ether of tetrabromobisphenol A. The epoxy equivalent is 430-450g/eq, and the bromine content is 18.5-20.5wt%.

HCA stands for 9,10-dihydro-9-oxa-10-phosphoranthracene-10-oxide produced by FORTE CHEMICAL CO., LTD with a trade name of DOPO.

Catalyst (curing accelerator) A represents ethyl triphenylphosphonium salt acetate acetate complex, 10% dissolved in methanol.

Catalyst (curing accelerator) B represents 2-methylimidazole (2MI), 10% dissolved in methyl ethyl ketone.

Nitrogen-containing curing agent A represents dicyandiamide, 10% soluble in dimethylformamide.

Nitrogen-containing curing agent B is produced by Hitachi Chemical, Japan, and its trade name is melan 9000 ^TM70 .

Nitrogen-containing curing agent C is the nitrogen-containing curing agent prepared in Synthesis Example 5.

Curing agent D is produced by Changchun Artificial Resin Factory, the trade name is BEH510, and the active hydrogen equivalent is 105-110g/eq.

The epoxy equivalent (EEW, Epoxy Equivalent Weight), varnish viscosity, and solid content used in this article are measured according to the following test methods:

(1) Epoxy equivalent: dissolve the epoxy resin in a solvent of chlorobenzene:chloroform=1:1, titrate with HBr/glacial acetic acid, and measure it according to ASTM D1652 method, wherein the indicator is crystal violet.

(2) Viscosity: the phosphorus-containing epoxy resin varnish was placed in a constant temperature bath at 25° C. for 4 hours, and measured at 25° C. with a Brookfield viscometer.

(3) Solid content: get 1 gram of the varnish sample that contains phosphorus-containing epoxy resin of the present invention, bake 60 minutes at 150 ℃ the weight percentage of the measured non-volatile matter.

Below, the present invention will be described in more detail through the following synthesis examples and examples, but the scope of the present invention is not limited to the following synthesis examples and examples.

Synthesis Example 1: Synthesis of Phosphorous Resin A

Put epoxy resin 1 (1000 grams) and HCA in a 3000ml five-necked glass reactor equipped with an electric heating mantle, temperature controller, electric stirrer and stirring rod, nitrogen inlet, thermocouple, water-cooled condenser, and addition funnel (400g), feed nitrogen and heat to 120 ° C, after epoxy resin 1 and HCA are completely melted, vacuumize the above raw materials to dry, then feed nitrogen and vacuum, repeat the above steps 2 times. Then the temperature of the reactor was lowered to 85-90° C., and catalyst A (6.0 g) was added. Start the mixer to stir the resin and catalyst evenly and blow nitrogen. The resulting mixture was heated to 160°C for 10 minutes. It was found that the reactants released heat gradually and continued to heat up to 180° C., and then kept at this temperature for 3 hours to obtain phosphorus-containing resin A, which had an epoxy equivalent of 453 g/eq and a theoretical phosphorus content of 4.1 wt%.

Synthesis example 2-4

Use the ingredients listed in Table 1 below and the listed weights to react according to the similar method of Synthesis Example 1, but after the reaction is over, add the solvent listed in Table 1 to the obtained epoxy resin to obtain the phosphorus-containing resin. Table 2 shows the epoxy equivalent, solid content and theoretical phosphorus content of the phosphorus-containing resins obtained in Synthesis Examples 2-4.

Table 1 Synthesis Example 2-4 Synthesis Formula Synthesis example 2 Synthesis example 3 Synthesis Example 4 Phosphorous resin B Phosphorous resin C Phosphorous resin D Epoxy resin 1 (g) 1000 Epoxy 2 (g) 1000 454.5 Epoxy 3 (g) 448.8 HCA (grams) 320 320 145.5 Bisphenol-A (grams) 139.3 Curing Accelerator A (g) 6.0 6.0 5.4 Ethyl Propylene Glycol Monoether (ml) 450 300 520.0 Acetone (ml) 450 595

Table 2 Property analysis of phosphorus-containing epoxy resin Phosphorous resin B Phosphorous resin C Phosphorous resin D Epoxy equivalent (g/eq) 403 378 451 solid content 59.8% 60.1% 59.7% Theoretical phosphorus content 3.48% 3.48% 1.76%

Synthesis example 5: Synthesis of nitrogen-containing curing agent C

Put 1269 grams of phenol, 541.5 grams of 37.4% formaldehyde, and melamine into a 3000ml five-neck glass bottle equipped with an electric heating mantle, temperature controller, electric stirrer and stirring rod, nitrogen inlet, thermocouple, water-cooled condenser, and addition funnel. 204 grams, 10.2 grams of triethylamine. Raise the temperature to 80-85°C and react for 3 hours. Add 204 grams of melamine and react for another 1 hour. After the reaction was completed, the temperature was gradually raised to 100°C to remove water, and then the temperature was raised to 120-125°C for 2 hours of reaction. After the reaction, unreacted phenol and reaction condensation water were slowly evaporated under normal pressure, and finally kept at 180° C. under vacuum for 1 hour. The resulting product was a total of 984 grams of nitrogen-containing curing agent C. The theoretical nitrogen content is 13.4wt%, and the active hydrogen equivalent is 125g/eq.

Examples 1-7 and Comparative Example 1

In a container equipped with a stirrer and a condenser at room temperature, the phosphorus-containing resins B, C and D, curing agent, curing accelerator and solvent synthesized in the synthesis examples 2 to 4 were prepared according to the proportions shown in Table 3 to form a ring Oxygen resin varnish.

table 3 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative example 1 Varnish formulation Phosphorous resin B (g) 150 Phosphorous resin C (g) 150 150 150 Phosphorous resin D (g) 200 200 200 Epoxy 4 (grams) 153 147 147 147 Epoxy resin 5 (grams) 125 Curing agent A 26.5 Curing agent B 65 50 58 Curing agent C 65 50 Curing agent D 65 50 Curing Accelerator B 1.8 2.4 0.9 0.6 0.6 0.6 0.6 0.6

Impregnate the glass fiber cloth with the prepared epoxy resin varnish, dry the impregnated glass fiber cloth at 150°C for 120 minutes to obtain a prepreg, and then pass it through DSC (Differential Scan Calorimeter, TA2910) (temperature range is 50-250°C , the heating rate is 20°C/min) to test the glass transition temperature of the obtained prepreg, and determine its flame retardancy by burning test (it is based on the method of UL746, the prepreg test piece is cut into 12.5mm×1.3mm There are 5 pieces of samples of different sizes, and each piece burns 2 times, and the total of 10 times of burning does not exceed 50 seconds, and the maximum single time does not exceed 10 seconds, which means that the burning test has passed). The results are shown in Table 4:

Table 4 Flame retardancy and glass transition temperature of the film after baking at 150°C for 120 minutes Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative example 1 Average burning time (seconds) 2～3 0～1 combustion 2～3 2～3 combustion 5～6 2～3 Tg(°C) 191.8 195.3 195.5 195.3 193.5 192.6 189.1 134.8

Laminate eight pieces of prepreg, place a piece of 35μm copper foil on top and bottom, press at 185°C and 25kg/ ^cm2 pressure to form a laminate of epoxy resin and glass fiber cloth, and analyze the physical properties of each laminate , and the results are shown in Table 5:

table 5 Analysis Project Conditions and Specifications Example 1 Example 4 Example 7 Comparative example 1 combustion test UL94-VO pass pass pass pass Solder resistance 288°C specification > 300 seconds pass pass pass fail Peel strength IPC specification > 8 lb/in 8.9 8.6 8.7 9.3 surface resistance IPC specification＞10 ¹⁰ Ω 2.68×10 ¹⁵ 1.98×10 ¹⁵ 2.63×10 ¹⁵ 3.57×10 ¹⁵ volumetric impedance IPC specification <10 ¹⁰ Ω 0.89×10 ¹³ 1.81×10 ¹³ 1.16×10 ¹⁴ 1.06×10 ¹⁴ Dielectric constant IPC specification <5.4 4.7 4.8 4.7 4.7 Dissipation coefficient - 0.022 0.021 0.020 0.020

Examples 8-11 and Comparative Example 2

In a container equipped with a stirrer and a condenser at room temperature, prepare the epoxy resin varnish according to the proportions shown in Table 6.

Table 6 Example 8 Example 9 Example 10 Example 11 Comparative example 2 Phosphorous resin A (g) 105 Phosphorous resin B (g) 150 Phosphorous resin C (g) 150 Phosphorous resin D (g) 200 Epoxy 4 (g) 153 147 147 Epoxy 5 (g) 125 Curing agent A (g) 26.5 Curing agent C (g) 68 65 68 96 Curing Accelerator B (g) 2.4 0.9 0.6 0.6 0.65

The epoxy resin compositions obtained in Examples 8, 10 and 11 and Comparative Example 2 above were coated on the rough surface of 18-micron copper foil with a thickness of 80 microns, and dried at 150°C. The resulting copper foil coated with epoxy resin is added to the upper and lower sides of the prepreg made of the epoxy resin composition of Example 1, and pressed at a temperature of 185°C and a pressure of 25kg/ ^cm2 to obtain a much Laminates. The physical properties of the multilayer board were analyzed, and the results are shown in Table 7.

Table 7 Analysis Project Conditions and Specifications Example 8 Example 10 Example 11 Comparative example 2 combustion test UL 94-VO pass pass pass pass Solder resistance IPC260℃ specification> 30 seconds pass pass pass pass Peel strength IPC specification > 6 lb/in (18μm) 7.6 7.4 8.0 8.4

From the above results, it can be seen that the phosphorus-containing epoxy resin of the present invention has better flame test performance and solder resistance than the phosphorus-free epoxy resin, but the peel strength does not decrease.

Claims (4)

1. fire-proof resin composition, it comprises:

(a) phosphorous resin is characterized in that, it contains the functional group as shown in the formula (A):

This functional group is by 9 of the epoxide group of Resins, epoxy and following formula (B), and the 10-dihydro-9-oxy is mixed-10-phosphorus anthracene-10-oxide compound

Reaction makes, or by the epoxide group and 9 of following formula (B) of Resins, epoxy, and mix-10 phosphorus anthracene-10-oxide compound and other of 10-dihydro-9-oxy contains compound bearing active hydrogen and react and make;

The Resins, epoxy of the phosphorous resin of wherein said manufacturing is selected from glycidyl ether, phenolic aldehyde polyglycidyl ether and the polyhydroxy phenol polyglycidyl ether of bis-phenol glycidyl ether, two diphenol glycidyl ether, dihydroxy-benzene glycidyl ether, the glycidyl ether that contains azo-cycle, dihydroxy naphthlene;

Described other contain compound bearing active hydrogen and are selected from amine, bisphenol resin, dihydroxy-benzene, polyhydroxy phenol resin and phenolic material;

The Resins, epoxy and 9 of the phosphorous resin of described manufacturing, the 10-dihydro-9-oxy is assorted-and 10-phosphorus anthracene-10-oxide compound and other contain the epoxide group equivalent of the reaction ratio of compound bearing active hydrogen for this Resins, epoxy: 9, the 10-dihydro-9-oxy is assorted-10-phosphorus anthracene-10-oxide compound Ahew: the Ahew of other active hydrogen-contg compounds is 100: (5～50): (0～45);

(b) solidifying agent shown in the following formula (C):

R in the formula ²Be hydrogen atom or [CH ₂-R ³] _nH, [CH ₂-R ³] _nN among the H is 0～20 integer; But at least one R ²It is not hydrogen atom;

R ' is NHR ², C _1-6Alkyl or phenyl,

R ³Be phenylene, naphthylidene or group with following formula structure:

In the formula A be-O-,-S-,-SO ₂-, CO-,-CH ₂-,-C (CH ₃) ₂-or group with following formula structure:

Or

Above-mentioned R ³Reach in the represented group of A, described aromatic group again can be by one or more hydroxyl, amino, carboxyl, C of being selected from _1-6The substituting group of alkyl replaces; And

(c) curing catalyst is selected from tertiary amine, three grades of phosphines, quaternary ammonium salt, quaternary alkylphosphonium salt, boron trifluoride complex, lithiumation thing and imidazolium compoundss and composition thereof;

The ratio of the epoxide group of the Resins, epoxy of the phosphorous resin of wherein said manufacturing and the Ahew of solidifying agent is: when the epoxide group equivalent of Resins, epoxy is 100%, the Ahew of solidifying agent is 20～140%, and the ratio of curing catalyst is 50～50 of a fire-proof resin composition gross weight, 000ppm.

2. according to the fire-proof resin composition of claim 1, wherein can comprise the Resins, epoxy that is selected from following cohort again: glycidyl ether, phenolic aldehyde polyglycidyl ether and the polyhydroxy phenol polyglycidyl ether of bis-phenol glycidyl ether, two diphenol glycidyl ether, dihydroxy-benzene glycidyl ether, the glycidyl ether that contains azo-cycle, dihydroxy naphthlene.

3. according to the fire-proof resin composition of claim 1, wherein can comprise the solidifying agent that is selected from amine, bisphenol resin, dihydroxy-benzene, polyhydroxy phenol resin and phenolic again.

4. the fire-proof resin composition of claim 1 is in order to make substrate or the semiconductor sealing material that adhesive sheet, matrix material, veneer sheet, printed circuit board (PCB), Layer increasing method are used.