CN1167732C - Resin curing agent containing phosphorus and nitrogen and flame-retardant epoxy resin composition containing same - Google Patents

Abstract

The present invention relates to a phosphorus and nitrogen containing resin curing agent having the formula: in which I or a hydrogen atom but at least one R²Is not a hydrogen atom; r¹Represents NHR²、C_1-6Alkyl or phenyl; n represents an integer of 0 to 20; -R-represents phenylene, naphthylene or a group of formula: -Ph-A-Ph-wherein Ph represents phenyl and A represents-O-, -S-, -SO₂-、-CO-、-CH₂-、C(CH₃)₂-or a group of formula: in the group represented by R and A, the hydrogen atom of the aryl group is substituted or unsubstituted with one or more substituents selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group and a C1-6 alkyl group, see the formula II below. The invention also relates to a flame-retardant epoxy resin composition containing the curing agent. It has excellent heat resistance and flame retardancy.

Description

Resin curing agent containing phosphorus and nitrogen and flame retardant epoxy resin composition containing the curing agent

technical field

The invention relates to a novel resin curing agent, in particular to a phosphorus and nitrogen-containing resin curing agent, and also relates to a flame retardant epoxy resin composition containing the curing agent.

The flame retardant epoxy resin composition of the present invention does not contain halogen and antimony trioxide, has flame retardant characteristics up to UL94V-0 and has high heat resistance, and can be used as an adhesive sheet (bonding sheet or prepreg), composite Materials (composite), laminates, printed circuit boards, build-up substrates (build-up, Resin Coated Copper), semiconductor packaging materials (Epoxy Molding Compound), etc.

Background technique

Composite materials, especially epoxy resin composite materials, are widely used in various fields such as coating, electrical insulation, civil engineering and construction materials, and adhesives due to their easy processability, high safety, excellent mechanical properties and chemical properties. And laminated products, etc. Among them, the laminated board made of epoxy resin has strong adhesion to reinforcing materials such as glass fiber cloth, no volatile matter is produced during curing, and the molding shrinkage is small, so the obtained laminated board has a wide range of applications. Wide, excellent mechanical strength, good electrical insulation, good chemical resistance and other advantages, greatly improving the reliability of laminated boards, making epoxy laminated boards widely used in electro-oxygen and electronic products.

However, in order to meet the ever-improving requirements of finer lines and higher density in printed circuit boards, laminates are also required to have more excellent electrical properties, mechanical properties, and thermal processing resistance. For the currently common FR4 laminates, 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 Laminated board materials may crack or burst during the manufacturing and processing process. Therefore, various laminate materials emphasizing high thermal stability and high glass transition temperature are actively being developed one after another. In addition, another important property for laminates is their flame retardancy. In some places of use, such as airplanes, automobiles and public transportation, the combustion directly poses a threat to human body and life safety. Therefore, 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 with flame-isolated flame-reducing properties. For epoxy resin/glass fiber (or organic fiber) laminates, use halogen-containing compounds, especially bromine-containing epoxy resins and curing agents, and use flame retardants such as antimony trioxide In order to meet the stringent requirements for the flame retardancy of laminated boards (such as UL 94V-0 rating). Generally, epoxy resins need to contain bromine content as high as 17% to 21%, and use antimony trioxide or other flame retardants together to reach the UL 94V-0 level. However, the use of high bromine content epoxy resins or antimony trioxide will undoubtedly pose some dangers to humans.

First of all, antimony trioxide has been listed as a carcinogen; on the other hand, bromine will not only produce corrosive bromine radicals and hydrogen bromide during combustion, but also aromatic compounds with high bromine content will produce severe Toxic brominated furans and brominated dioxins seriously affect 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 laminates. In particular, FR-4 epoxy fiberglass laminates are used in large quantities, and the demand is stronger.

As a new generation of environmentally friendly flame retardants, phosphorus compounds have been widely studied and applied. For example, directly use 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 properties. However, directly adding these compounds in 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 migration (migration) will directly affect the quality of the resin substrate. Features: such as electrical properties, adhesive strength, etc., causing 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 a formula for flame retardant laminates, such as US Patent No. 5,376,453, using Phosphate esters with epoxy groups are combined with nitrogen-containing ring-shaped 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 ester epoxides are added; US Patent 5,458,978 No. uses 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 UL94V-0 (42 seconds relative to the critical value of 50 Second). U.S. Patent No. 4,973,631 and U.S. Patent No. 5,086,156 use trihydrocarbylphosphine chlorides with active hydrogen substituents (such as amino groups) alone or in combination with other ammonia curing agents for the curing of epoxy resins; however, the use of curing agents to introduce phosphorus into the resin has the disadvantage of low phosphorus content, and there is no measurement of the actual flame retardant effect in these two patents.

purpose of invention

The present invention aims at the above, improves the shortcomings of the current technology, and aims to improve the basic properties of electrical and mechanical properties and reduce costs, thus completing the present invention.

Therefore, primary purpose of the present invention is to provide a kind of resin curing agent containing phosphorus and nitrogen;

Another object of the present invention is to provide a kind of flame retardant epoxy resin composition containing said curing agent;

Another object of the present invention is to provide the described flame retardant epoxy resin composition for use in the manufacture of adhesive sheets, composite materials, laminates, printed circuit boards, substrates for build-up methods, and semiconductor packaging materials application.

The present invention relates to a kind of resin curing agent containing phosphorus and nitrogen, which has the following formula:

or hydrogen atom

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

n represents an integer from 0 to 20;

-R- represents phenylene, naphthylene or a group of the formula:

-Ph-A-Ph-

In the formula, Ph represents phenyl, and A represents -O-, -S-, -SO ₂ -, -CO-, -CH ₂ -, C(CH ₃ ) ₂ - or a group of the following formula:

In the above-mentioned groups represented by R and A, the hydrogen atom of the aryl group is substituted or unsubstituted by one or more substituents selected from hydroxyl, amino, carboxyl and C _1-6 alkyl.

The present invention also relates to a flame-retardant epoxy resin composition, which includes (A) epoxy resin, (B) the above-mentioned phosphorous and nitrogen-containing resin curing agent, and (C) curing accelerator.

In the flame retardant epoxy resin composition of the present invention, the contained epoxy resin can be any epoxy resin, which is selected from 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.

Glycidyl ethers of bisphenols include, for example, bisphenol A glycidyl ether, bisphenol F glycidyl ether, bisphenol AD glycidyl ether, bisphenol S glycidyl ether, tetramethyl bisphenol A glycidyl ether, tetramethyl Bisphenol F glycidyl ether, tetramethyl bisphenol AD glycidyl ether, tetramethyl bisphenol S glycidyl ether.

Bis-diphenol glycidyl ethers include: for example, 4,4'-diphenol glycidyl ether, 3,3'-dimethyl-4,4'-diphenol glycidyl ether, 3,3',5,5'- Tetramethyl-4,4'-diphenol glycidyl ether.

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

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

Phenyl 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, tris(4-hydroxyphenyl)butane polyglycidyl ether, tris(3-methyl-4-hydroxyphenyl)methane polyglycidyl ether, tris(3,5-dimethyl-4 -Hydroxyphenyl)methane polyglycidyl ether, tetrakis(4-hydroxyphenyl)ethane polyglycidyl ether, tetrakis(3,5-dimethyl-4-hydroxyphenyl)ethane polyglycidyl ether, bicyclic Pentene-phenolic polyglycidyl ether.

The nitrogen-containing ring glycidyl ether includes, for example, triglycidyl ether of isocyanurate and triglycidyl ether of cyanurate.

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

These epoxy resins may be used alone or in admixture of two or more.

Among them, bisphenol A polyglycidyl ether, phenolic polyglycidyl ether, three (4-hydroxyphenyl) methane polyglycidyl ether, dicyclopentene-phenolic polyglycidyl ether and tetrafunctional four (phenyl) -4-hydroxy)ethane polyglycidyl ether or mixtures thereof.

The epoxy resin curing agent in the flame retardant epoxy resin composition of the present invention is preferably the compound of the following formula:

In the formula, b is an integer from 0 to 20.

The flame-retardant epoxy resin composition of the present invention may further include other halogen-free curing agents in addition to the phosphorus- and nitrogen-containing resin curing agent of the present invention. The other halogen-free curing agents include amines, bisphenol resins, quinone, polyhydric phenol resins, and phenolic resins.

Amines include, for example, dicyandiamide, diaminodiphenylmethane.

Bisphenol resins comprising, for example, the formula HO-Ph-X-Ph-OH (where Ph represents phenylene, X= _CH2 -C( _CH3 ) ₂ , -O-, -S-, -CO- and -SO ₂ -) Compounds such as 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.

Poly(hydroxyphenol) resins include, for example, tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane , tris(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 flame retardant epoxy resin composition of the present invention, the addition amount of curing agent is determined according to the reactive hydrogen equivalent of each curing agent and the epoxy equivalent of epoxy resin, and the suitable equivalent ratio is to the epoxy equivalent of epoxy resin. Oxygen equivalent 100%, the reactive hydrogen equivalent of curing agent is 20 to 140%, more suitable equivalent ratio is to the epoxy equivalent of epoxy resin 100%, the reactive hydrogen equivalent of curing agent is 40 to 95%, A more suitable equivalent ratio is 100% of the epoxy equivalent of the epoxy resin, and 50 to 95% of the reactive hydrogen equivalent of the curing agent.

In the flame retardant epoxy resin composition of the present invention, if other halogen-free curing agents are used, the usage ratio of the phosphorus- and nitrogen-containing epoxy resin curing agent of the present invention to the other halogen-free curing agents 5:95 to 100:0, preferably 20:80 to 100:0, more preferably 25:75 to 100:0. If the content of the phosphorus- and nitrogen-containing epoxy resin curing agent of the present invention is too low, it will easily cause insufficient flame retardancy and heat resistance.

The curing accelerator in the flame retardant epoxy resin composition of the present invention is selected from tertiary amines, tertiary phosphines, quaternary ammonium salts, quaternary phosphonium salts, boron trifluoride complexes, lithium compounds and imidazole compounds and mixture.

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

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

Suitable organic aromatic solvents are for example: toluene, xylene.

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

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

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

Suitable ester solvents are, for example, ethyl acetate, ethyl isopropionate, and ethyl propylene glycol monomethyl ether.

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

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

The present invention further relates to the application of the flame retardant composition in the manufacture of adhesive sheets, composite materials, laminates, printed circuit boards, substrates for build-up methods and semiconductor packaging materials.

The flame retardant epoxy resin composition of the present invention can be made into a laminated body of copper foil, a fiber support and the flame retardant epoxy resin composition of the present invention by a generally known method in the industry.

The flame retardant epoxy resin composition of the present invention is used to prepare a varnish, and impregnated fiber substrates such as organic or inorganic fiber substrates, such as glass fibers, metal fibers, carbon fibers, aramid fibers, boron and cellulose, will impregnate the impregnated fiber substrates. The material is heated and dried to obtain a dry prepreg (prepreg). The prepreg can be further molded into a composite material laminate, or used alone for the adhesive layer of other films, or one or more of them are combined, and copper foil is placed on the upper side or the upper and lower sides, The prepreg or its composition is heated under pressure, and the obtained laminate composite material exceeds the standard of current products in terms of dimensional stability, chemical resistance, corrosion resistance, moisture absorption and electrical properties, suitable for Used in the manufacture of electrical products used in electronics, space, transportation, etc., such as printed circuit boards and multilayer circuit boards.

The flame retardant epoxy resin composition of the present invention can also be formulated into a varnish, coated on a copper foil, and heated and dried to obtain a dry copper foil adhesive (RCC, Resin Coated Copper). The copper foil adhesive can be stored for several months at room temperature, and has good storage stability. The RCC can be further formed into a composite material laminate, or used alone as an adhesive layer of other films, or one or more of them can be combined, and layers can be added layer by layer on the upper side or the upper and lower sides. Pressing (build-up), the obtained laminate composite material exceeds the standard of current products in terms of dimensional stability, chemical resistance, corrosion resistance, moisture absorption and electrical properties, and is suitable for manufacturing and using in electronics. , space, transportation and other multi-layer printed circuit boards.

The suitable curing reaction temperature of the flame retardant epoxy resin composition of the present invention is generally 20 to 350°C, preferably 50 to 300°C, more preferably 100 to 250°C, most preferably 120 to 220°C. If the temperature is too high, side reactions are likely to occur and it is difficult to control the reaction rate, 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 needs of high temperature use.

The flame retardant epoxy 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 retardant and heat resistance properties of the epoxy resin.

Detailed ways

The following synthesis examples and examples will be used to further illustrate the present invention, 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: Represents the diglycidyl ether of bisphenol A produced by Changchun Artificial Resin Factory and sold under the trade name BE188EL. Its epoxy equivalent is between 185 and 195g/eq, its hydrolyzable chlorine is below 200ppm, and its viscosity is between 11000 to 15000cps/25°C.

Epoxy resin 2: represents polyglycidyl ether of cresol-aldehyde condensate produced by Changchun Artificial Resin Factory and sold under the trade name CNE200ELD, and its epoxy equivalent is between 190 and 210 g/eq.

Epoxy resin 3: represents phenolic polyglycidyl ether produced by Changchun Artificial Resin Factory and sold under the trade name PNE177, and its epoxy equivalent is between 170 and 190 g/eq.

Epoxy Resin 4: Represents the diglycidyl ether of tetrabromobisphenol A produced by Changchun Artificial Resin Factory and sold under the trade name BEB530A80, with an epoxy equivalent of 430 to 450 g/eq and a bromine content of 18.5 to 20.5 wt %.

Epoxy Resin 5: Produced by Changchun Artificial Resin Factory, the trade name is BE501, and its epoxy equivalent is between 490 and 510g/eq.

Curing agent A: stands for dicyandiamide, 10% soluble in dimethylformamide.

Curing agent B: a phosphorus- and nitrogen-containing epoxy resin curing agent represented by the following formula of the present invention.

In the formula, b is an integer from 0 to 20.

Curing Agent C: Produced by Changchun Artificial Resin Factory, the trade name is BEH510, and the active hydrogen equivalent is between 105 and 110g/eg.

Curing accelerator A: represents 2-methylimidazole (2MI), 10% dissolved in methyl ethyl ketone.

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

(1) Epoxy equivalent: the epoxy resin is dissolved in a solvent of chlorobenzene:chloroform=1:1, titrated with HBr/glacial acetic acid, measured according to the method of ASTM D1652, 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 containing the phosphorus-containing epoxy resin of the present invention, and bake it at 150° C. for 60 minutes to measure the weight percentage of the non-volatile matter.

Synthesis Example 1: Synthesis of phosphorus and nitrogen-containing resin curing agent (curing agent B):

Put 1410 grams (15 mole) of phenol and 92% polyoxymethylene in a 3000ml five-neck glass reactor equipped with an electric heating mantle, a temperature controller electric stirrer and a stirring rod, a nitrogen inlet, a thermocouple, a water-cooled condenser, and an addition funnel 244.7 grams (7.5 mole), benzoguanamine (benzoguanamine) 337 grams (1.8 mole), 9,10-dihydro-9-oxa-10-phosphoranthracene-10-oxide (HCA) 259 grams (1.2 mole ), 11.2 grams of oxalic acid, after melting, vacuumize to make the above raw materials dry, then pass into nitrogen, repeat vacuumize and pass into nitrogen program twice. Raise the temperature to 100 to 110°C and react for 3 hours. Then the temperature was raised to 120 to 125° C. for 2 hours. After the reaction is completed, the unreacted phenol and reaction condensation water are slowly evaporated at normal pressure, and finally kept at 180° C. under vacuum for 1 hour. The resulting product is the phosphorus and nitrogen-containing resin curing agent (curing agent B) of the present invention.

After analysis, the softening point is 161°C, the theoretical nitrogen content is 10.0wt%, the phosphorus content is 2.93wt%, and the active hydrogen equivalent is 210g/eq.

Embodiment 1 to b and comparative example 1

In a container equipped with a stirrer and a condenser at room temperature, the curing agent B synthesized in Synthesis Example 1, other curing agents, epoxy resin, curing accelerator and solvent were prepared into an epoxy resin according to the ratio shown in Table 1 varnish.

Table 1

The prepared epoxy resin varnish is impregnated with glass fiber cloth, dried at 180°C for 120 minutes to form a prepreg, and the glass transition temperature (Temperature The range is 50 to 250°C, the heating rate is 20°C/min), and its flame retardancy is measured by a combustion test. It is based on the method of UL746, and the prepreg test piece is cut into 5 pieces of 12.5mm×1.3mm in size. The piece burns 2 times, and the sum 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 2:

Table 2 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative example 1 combustion test pass pass pass pass pass pass pass Tg(°C) 163 160 151 148 158 144 132

Laminate eight pieces of prepreg, place a piece of 35μm copper foil on top and bottom of it, 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 as shown in Table 3

table 3 Analysis Project Conditions and Specifications Example 3 Example 4 Comparative example 1 Solder resistance 288°C specification > 300 seconds pass pass fail Peel strength Specification＞8lb/in 8.92 8.56 9.25 surface resistance Specification＞10 ¹² 2.5*10 ¹⁵ 3.3*10 ¹⁵ 2.9*10 ¹⁵ volume resistance Specifications > 10 ¹⁰ 11*10 ¹³ 2.0*10 ¹³ 1.2*10 ¹⁴ Dielectric constant Specification <5.4 4.45 4.81 4.72 Dissipation factor -- 0.021 0.023 0.022

Examples 7 to 10 and Comparative Example 2

In a container equipped with a stirrer and a condenser at room temperature, prepare the epoxy resin varnish with the ingredients shown in Table 4 according to the ratio shown in Table 4.

Table 4

The epoxy resin compositions obtained in Examples 7, 8 and 10 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 obtained 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 multilayer plate. The physical properties of the multilayer board were analyzed, and the results are shown in Table 5.

table 5 Analysis Project Conditions and Specifications Example 7 Example 8 Example 10 Comparative example 2 combustion test UL 94-V0 pass pass pass pass Solder resistance 288°C specification > 300 seconds pass pass pass fail Peel strength IPC specification＞6lb/in(18μm) 7.3 7.9 8.1 8.4

From the above results, it can be seen that the resin curing agent containing phosphorus and nitrogen of the present invention has better flame test and soldering resistance than the curing agent without phosphorus and nitrogen, but the peel strength has not decreased.

Claims (8)

1. the resin curing agent of a phosphorous and nitrogen, it has following formula:

In the formula Or hydrogen atom

But at least one R ²It is not hydrogen atom;

R ¹Expression NHR ², C _1-6Alkyl or phenyl;

N represents 0 to 20 integer;

-R-represents the group of penylene, naphthylene or following formula:

-Ph-A-Ph-

Ph represents phenyl in the formula, A represents-O-,-S-,-SO ₂-,-CO-,-CH ₂-,-C (CH ₃) ₂-or the group of following formula:

In the represented group of above-mentioned R and A, the hydrogen atom of aryl is selected from hydroxyl, amino, carboxyl and C by one or more _1-6The substituting group of alkyl replaces or is not substituted.

2. the resin curing agent of phosphorous and nitrogen as claimed in claim 1, it has following formula:

B is 0 to 20 integer in the formula.

3. a difficult combustible epoxy resin composition comprises (A) Resins, epoxy, (B) resin curing agent of claim 1 or 2 described phosphorous and nitrogen, and (C) curing catalyst;

Wherein said Resins, epoxy 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.

4. difficult combustible epoxy resin composition as claimed in claim 3, wherein this 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.

5. difficult combustible epoxy resin composition as claimed in claim 3, wherein the Resins, epoxy epoxy equivalent (weight) in composition (A) is 100%, the hardener dose of composition (B) counts 20 to 140% with its reactive behavior hydrogen equivalent.

6. difficult combustible epoxy resin composition as claimed in claim 3, wherein the curing catalyst consumption of composition (C) is 50 to 50 of a composition epoxy resin gross weight, 000ppm.

7. difficult combustible epoxy resin composition as claimed in claim 3, it can further comprise the solidifying agent of amine, bisphenol resin, dihydroxy-benzene, polyhydroxy phenol resin and phenolic.

8. the described difficult combustible epoxy resin composition of claim 3 is being used for making the substrate that adhesive sheet, matrix material, laminated plates, printed circuit board (PCB), Layer increasing method use and the application of semiconductor sealing material.