TW201741387A - Flame retardant resin composition, thermosetting resin composition, prepreg plate and composite metal substrate comprising a brominated flame retardant (BFR) and a halogen-free epoxy resin - Google Patents

Abstract

The present invention provides a flame retardant resin composition, a thermosetting resin composition, a prepreg plate and a composite metal substrate, wherein the flame retardant resin composition comprises a brominated flame retardant (BFR) and a halogen-free epoxy resin; the BFR comprises brominated phenolic compounds and resins therefor; and the compositions also comprise sulfur-containing flame retardant and/or phosphor-containing flame retardant. The BFR and the phosphor-containing flame retardant contained in the flame retardant resin composition produce a synergistic effect on flame-retardant effects, which can improve the flame retardant performance of the resin composition. Moreover, the cured product in the flame retardant resin composition is excellent in heat resistance, water-resistance, bondability, mechanical properties and electrical properties; therefore, the disclosed provides an environment-friendly flame retardant composition with a higher economic benefit.

Description

Flame retardant resin composition, thermosetting resin composition, prepreg and composite metal substrate

The invention belongs to the field of flame retardant materials, and relates to a flame retardant resin composition, a thermosetting resin composition, a prepreg and a composite metal substrate.

Electronic products represented by mobile phones, computers, video cameras, and electronic game machines, household and office electrical products represented by air conditioners, refrigerators, television images, and audio equipment, and various products used in other fields, for safety, a large part of Products are required to have varying degrees of flame retardant properties.

In order to achieve the required flame retardant properties or grades of the products, conventional techniques often use halogen-containing flame retardant substances in the material system, for example, adding brominated bisphenol A, brominated bisphenol A ring to the system material. An organic chemical substance such as an oxygen resin having a relatively high bromine content or a relatively high halogen content. Although these halogen-containing flame retardants are excellent in flame retardancy, they are used in a relatively large amount, for example, in the preparation of a copper clad laminate, To achieve better flame retardant effect, when using bromine-containing flame retardant, ensure that the bromine content of the flame retardant and epoxy resin composition is above 20%, which results in higher bromine content in the product. High halogen content can also have some adverse effects, such as high temperature or burning, which will produce refractory harmful substances such as dioxin-like organic halogen chemicals, which pollute the environment and affect human and animal health.

Therefore, how to reduce the amount of the flame retardant and ensure the flame retardant effect is an urgent problem to be solved in the art.

In view of the deficiencies of the prior art, an object of the present invention is to provide a flame retardant resin composition, a thermosetting resin composition, a prepreg, and a composite metal substrate.

In order to achieve the object, the present invention adopts the following technical means: In one aspect, the present invention provides a flame retardant resin composition comprising a bromine-containing flame retardant and a halogen-free epoxy resin; The agent is a bromine-containing phenolic compound and an epoxy resin thereof; and the above composition also contains a sulfur-containing flame retardant and/or a phosphorus-containing flame retardant.

In the flame retardant resin composition of the present invention, a bromine-containing flame retardant is blended with a sulfur-containing flame retardant and/or a phosphorus-containing flame retardant to form a synergistic flame retardant, and the halogen-free epoxy resin can be used to make the composition thereof. The cured product has good flame retardancy, heat resistance, water resistance, high peel strength, and thermal decomposition temperature.

It is necessary to include a bromine-containing flame retardant in the flame retardant resin composition of the present invention, and one or both of the sulfur-containing flame retardant and the phosphorus-containing flame retardant may be contained in the flame retardant resin composition. The flame retardant resin composition comprises a bromine-containing flame retardant, a sulfur-containing flame retardant, and a A phosphorus flame retardant and a halogen-free epoxy resin, and the bromine-containing flame retardant is a bromine-containing phenol compound and an epoxy resin thereof.

Desirably, the content of bromine in the flame retardant resin composition is 10% by weight or less, for example, 10%, 9%, 8.5%, 8%, 7%, 7.5%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.3%, 0.1%, etc., ideally 1-10%.

Desirably, the content of sulfur element in the flame retardant resin composition is 0.2% by weight or more, for example, 0.2%, 0.25%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 1.8%, 2%, etc., ideally 0.2-1%.

Desirably, the content of phosphorus element in the flame retardant resin composition is 0.2% by weight or more, for example, 0.2%, 0.25%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 1.8%, 2%, 2.5%, 3%, 4%, 5%, etc., desirably 0.2-2%.

In the range of bromine, sulfur and phosphorus content defined by the present invention, the bromine-containing flame retardant and the sulfur-containing flame retardant and/or the phosphorus-containing flame retardant are coordinated to synergistically enhance the flame retardancy of the resin composition. It can ensure that the resin composition has good flame retardant properties, and can control the bromine element content to a lower range, thereby reducing the possibility of generating harmful substances due to high temperature, and in the content range, the flame retardant resin composition is prepared. The performance of all aspects of the copper clad laminate can be optimized, with good heat resistance, water resistance, high thermal decomposition temperature, etc., so that the comprehensive performance of the copper clad laminate can be improved.

The traditional bromine-containing flame retardant should maintain a bromine content of more than 20% when used in the resin composition to achieve a good flame retardant effect to ensure the flame retardant properties of the copper clad laminate. Adding a small amount of sulfur-containing flame retardant and/or phosphorus-containing flame retardant to the resin composition to form a composite flame retardant for use in the resin composition, which can make the bromine-containing flame retardant and the sulfur-containing flame retardant and/or The flame retardant effect of the phosphorus flame retardant promotes each other, achieves the synergistic flame retardant effect, reduces the use amount of the bromine-containing flame retardant, saves cost, and can ensure the good heat resistance and water resistance of the copper clad laminate, and the high Thermal decomposition temperature, etc.

In the present invention, the bromine element content, the sulfur element content, and the phosphorus element content in the flame retardant resin composition are calculated based on 100% by weight of the flame retardant resin composition.

Desirably, the bromine-containing flame retardant is a brominated phenolic resin, a brominated phenolic epoxy resin, a brominated bisphenol A, a brominated bisphenol A derivative, a brominated bisphenol A type epoxy resin, and a tetrabromobisphenol. Any one or a combination of at least two of S, tetrabromobisphenol allyl ether, tribromophenol or pentabromophenol, preferably brominated bisphenol A, brominated bisphenol A derivative or brominated bisphenol A type Epoxy resin.

Desirably, the sulfur-containing flame retardant is terephthalene and/or 4,4'-diaminodiphenyl disulfide, preferably terephthalene.

Desirably, the aforementioned phosphorus-containing flame retardant is DOPO etherified bisphenol A, DOPO modified epoxy resin, tris(2,6-dimethylphenyl)phosphine, tetra-(2,6-dimethylphenyl). Hydroquinone diphosphate, resorcinol tetraphenyl diphosphate, triphenyl phosphate, bisphenol A bis(diphenyl phosphate), phosphazene flame retardant, 10-(2,5-dihydroxyl Phenyl)-10-hydrogen-9-oxa-10-phosphinophen-10-oxide, 10-(2,5-dihydroxynaphthyl)-10-hydro-9-oxa-10-phosphanol- Any one or a mixture of at least two of 10-oxide or 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide flame retardant.

Other flame retardant materials may be added to the flame retardant composition of the present invention as needed.

Desirably, the aforementioned other flame retardant material is any one or a combination of at least two of an organic antimony flame retardant, a chlorine-containing organic flame retardant, a nitrogen-containing organic flame retardant, or an inorganic flame retardant.

Desirably, the aforementioned chlorine-containing organic flame retardant is any one or a combination of at least two of dioctyl tetrachlorophthalate, chlorinic anhydride, chlorinic acid or tetrachlorobisphenol A.

Desirably, the aforementioned nitrogen-containing organic flame retardant is any one or a combination of at least two of dicyandiamide, biuret or melamine.

Desirably, the inorganic flame retardant is any one or a combination of at least two of aluminum hydroxide, magnesium hydroxide, antimony trioxide or zinc borate.

Desirably, the halogen-free epoxy resin is selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, bisphenol A novolac epoxy resin, o-cresol novolac epoxy resin. At least one or a mixture of at least two of a dicyclopentadiene type epoxy resin, an isocyanate type epoxy resin, or a biphenyl type epoxy resin.

Desirably, the foregoing epoxy resin has a mass percentage of 70-90%, such as 70%, 73%, 75%, 78%, 80%, 83%, 85%, 88% or 90%.

On the other hand, the present invention provides a thermosetting resin composition comprising the flame retardant resin composition as described above.

Desirably, the aforementioned thermosetting resin composition also contains a curing agent.

Desirably, the aforementioned curing agent is selected from any one or a combination of at least two of dicyandiamide, phenolic resin, aromatic amine, acid anhydride, active ester curing agent or active phenol curing agent.

Desirably, the thermosetting resin composition further includes a curing accelerator; desirably, the curing accelerator is any one or a mixture of at least two of an imidazole curing accelerator, an organic phosphine curing accelerator or a tertiary amine curing accelerator. .

Desirably, the aforementioned imidazole compound is selected from the group consisting of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, Any one of 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole or 1-cyanoethyl-2-methylimidazole or A mixture of at least two, ideally 2-methylimidazole.

In another aspect, the present invention provides a prepreg which is obtained by impregnating or coating a thermosetting resin composition described above on a substrate.

Desirably, the substrate may be a glass fiber substrate, a polyester substrate, a polyimide substrate, a ceramic substrate or a carbon fiber substrate.

In the present invention, the specific process conditions for impregnation or coating are not particularly limited. "Prepreg sheets" are also "bonded sheets" well known to those skilled in the art.

A composite metal substrate obtained by sequentially coating a metal layer on at least one of the prepreg sheets, overlapping, and pressing.

Desirably, the material of the surface metallization layer is an alloy of aluminum, copper, iron, and any combination thereof.

Desirably, the composite metal substrate is CEM-1 copper clad laminate, CEM-3 copper clad laminate, FR-4 copper clad laminate, FR-5 copper clad laminate, CEM-1 aluminum substrate, CEM-3 aluminum substrate, FR-4 aluminum substrate or Any of the FR-5 aluminum substrates.

A circuit board is formed by processing a circuit on a surface of the aforementioned composite metal substrate.

Compared with the prior art, the present invention has the following effects: the bromine-containing flame retardant in the flame retardant resin composition of the present invention has a synergistic effect on the flame retardant effect with the sulfur-containing flame retardant and/or the phosphorus-containing flame retardant. The flame retardancy of the resin composition can be enhanced. The cured product of the flame retardant resin composition of the present invention has good heat resistance, water resistance, adhesion, mechanical properties and electrical properties, and is a flame retardant composition which is economical and environmentally friendly. The copper-clad board prepared from the composition has a thermal decomposition temperature (5% weight loss) of up to 353 ° C or more, a peel strength of 1.8 kg/mm ² or more, T-288>100 seconds, and a heat-resistant limit of immersion tin of 31 times or more. The saturated water absorption rate can reach 0.35% or less, and the flammability (UL-94) reaches the V-0 level.

The technical means of the present invention will be further described below by way of specific embodiments. It should be understood by those skilled in the art that the present invention is not to be construed as limited.

Example 1

100 g of liquid bisphenol A type epoxy resin having an epoxy equivalent of 186 g/eq was taken, and 26.4 g of brominated bisphenol A type epoxy resin having an epoxy equivalent of 400 g/eq and a bromine content of 48.5% and a sulfur content of 45 were added. After mixing 1.42 g of p-terphenyldithiol, a flame retardant resin mixture having a bromine content of 10% and a sulfur content of 0.5% was obtained, dissolved in an appropriate amount of acetone, and then 6.4 g of dicyandiamide and 0.1 g of 2- were added. After the methyl imidazole is fully dissolved, the standard copper clad plate conforming to the national standard, UL standard, etc. is prepared according to the general copper clad board production procedure, and the copper clad plate is called the copper clad plate A, and the performance test result of the copper clad plate A is obtained. As shown in Table 1.

Example 2

100 g of liquid bisphenol A type epoxy resin having an epoxy equivalent of 186 g/eq was taken, and 20.8 g of brominated bisphenol A and 25% of sulfur having a bromine content of 55% were added with a phenolic hydroxyl equivalent of 272 g/eq, a bromine content of 58.5%. After mixing 0.68 g of dithiol, a resin mixture having a bromine content of 10% and a sulfur content of 0.25% was obtained, and an appropriate amount of acetone was added to dissolve, and a phenolic hydroxyl equivalent of 105 g/eq of a novolak type phenolic resin of 47.4 g and 0.1 g of 2-methyl was added. After the imidazole is fully dissolved, the composition is prepared according to a general copper clad plate making process. The standard copper-clad board that meets the national standard, UL and other standards is called the copper-clad board B. The performance test results of the copper-clad board B are shown in Table 1.

Example 3

100 g of o-cresol novolac epoxy resin having an epoxy equivalent of 200 g/eq was taken, and 11.9 g of brominated bisphenol A type epoxy resin having an epoxy equivalent of 400 g/eq and a bromine content of 48.5% and a sulfur content of 14.8% were added. 2.1 g of 4,4'-diaminodiphenyldisulfide gave a resin composition having a bromine content of 5% and a sulfur content of 0.25%, dissolved in an appropriate amount of acetone, and added a linear form having a phenolic hydroxyl equivalent of 105 g/eq. After the phenolic resin curing agent 59.7g and 0.1g of 2-methylimidazole are fully dissolved, the standard copper-clad board which meets the national standard, UL standard, etc. is prepared according to the general copper-clad board preparation procedure, and the copper-clad board is called For the copper clad C, the performance test results of the clad copper C are shown in Table 1.

Example 4

100 g of liquid bisphenol A type epoxy resin having an epoxy equivalent of 186 g/eq was taken, and 31.0 g of a brominated bisphenol A type epoxy resin having an epoxy equivalent of 400 g/eq and a bromine content of 48.5% and a phosphorus content of 9.0 were added. After mixing 14g of tetrakis-(2,6-dimethylphenyl)resorcinol diphosphate, a flame retardant resin mixture having a bromine content of 10% and a phosphorus content of 1.0% is obtained, and an appropriate amount of acetone is added to dissolve, and then added. After 6.7 g of dicyandiamide and 0.1 g of 2-methylimidazole are sufficiently dissolved, a copper clad laminate is obtained according to a known method, and the copper clad laminate is referred to as a copper clad laminate D. The performance test results of the copper clad laminate D are shown in Table 1. .

Example 5

100 g of liquid bisphenol A type epoxy resin having an epoxy equivalent of 186 g/eq was taken, and 25.5 g of brominated bisphenol A having a phenolic hydroxyl equivalent of 272 g/eq and a bromine content of 58.5% and a phenolic hydroxyl equivalent of 300.0 g/eq were added. After mixing 20.0% of DOPO etherified bisphenol A having a phosphorus content of 10.0%, a flame retardant resin mixture having a bromine content of 10% and a phosphorus content of 1.5% is obtained, and an appropriate amount of acetone is added to dissolve, and then a phenolic hydroxyl equivalent is added. After fully dissolving 38.6 g of 105 g/eq novolac resin and 0.1 g of 2-methylimidazole, a copper clad laminate was obtained according to a known method, and the copper clad laminate was referred to as a copper clad laminate E. The performance test results of the copper clad laminate E are shown in the table. 1 is shown.

Example 6

100 g of liquid bisphenol A type epoxy resin having an epoxy equivalent of 186 g/eq was taken, and 44.8 g of brominated bisphenol A type epoxy resin having an epoxy equivalent of 400 g/eq and a bromine content of 48.5% and a phosphorus content of 3.0 were added. %, 72.5g of a general-purpose DOPO modified epoxy resin having an epoxy equivalent of 300g/eq is mixed, and a flame retardant resin mixture having a bromine content of 10% and a phosphorus content of 1.0% is obtained, and an appropriate amount of acetone is added to dissolve, and then added. After 9.7 g of dicyandiamide and 0.1 g of 2-methylimidazole are sufficiently dissolved, a copper clad laminate is obtained according to a known method, and the copper clad laminate is referred to as a copper clad laminate F. The performance test results of the copper clad laminate F are shown in Table 1. .

Example 7

100 g of liquid bisphenol A type epoxy resin having an epoxy equivalent of 186 g/eq was taken, and 9.3 g of brominated bisphenol A and a phenolic hydroxyl equivalent of 300.0 g/eq were added with a phenolic hydroxyl equivalent of 272 g/eq and a bromine content of 58.5%. After mixing 5.7 g of DOPO etherified bisphenol A having a phosphorus content of 10.0%, a flame retardant resin mixture having a bromine content of 5% and a phosphorus content of 0.5% was obtained, and an appropriate amount of acetone was added to dissolve, and then the phenolic hydroxyl equivalent was 105 g/ After fully dissolving 50.9 g of eq linear phenolic resin and 0.1 g of 2-methylimidazole, a copper clad laminate was obtained according to a known method, and the copper clad laminate was referred to as a copper clad laminate G. The performance test results of the clad copper clad G are shown in Table 1. .

Example 8

100 g of liquid bisphenol A type epoxy resin having an epoxy equivalent of 186 g/eq was taken, and 13.2 g of brominated bisphenol A type epoxy resin having an epoxy equivalent of 400 g/eq and a bromine content of 48.5% and a sulfur content of 45 were added. 1.43 g of para-phenylene disulfide and tetra-(2,6-dimethylphenyl)resorcinol double phosphorus with a phosphorus content of 10.0% After mixing 14.8 g of the acid ester, a flame retardant resin mixture having a bromine content of 5%, a sulfur content of 0.5%, and a phosphorus content of 1.0% was obtained, dissolved in an appropriate amount of acetone, and then 6.0 g of dicyandiamide and 0.1 g of 2 were added. After the methylimidazole was sufficiently dissolved, a copper clad laminate was obtained according to a known method, and the copper clad laminate was referred to as a copper clad laminate H. The performance test results of the clad copper clad sheet H are shown in Table 1.

Example 9

100 g of liquid bisphenol A epoxy resin having an epoxy equivalent of 186 g/eq was taken, and pentyl bromide A 11.2 g having a phenolic hydroxyl equivalent of 272 g/eq, a bromine content of 58.5%, and a benzene having a sulfur content of 45% were added. 0.6 g of dithiol and 300.0 g/eq of phenolic hydroxyl equivalent, and 19.8 g of DOPO etherified bisphenol A having a phosphorus content of 10.0% were mixed to obtain a bromine content of 5%, a sulfur content of 0.2%, and a phosphorus content of 1.5%. The flame retardant resin mixture is dissolved by adding an appropriate amount of acetone, and after further adding 44.3 g of a phenolic hydroxyl equivalent of 105 g/eq of a novolak type phenolic resin and 0.1 g of 2-methylimidazole, a copper clad laminate is obtained according to a known method. The copper clad laminate is called the copper clad laminate J, and the performance test results of the clad copper clad J are shown in Table 1.

Example 10

100 g of liquid bisphenol A type epoxy resin having an epoxy equivalent of 186 g/eq was taken, and 7.6 g of brominated bisphenol A type epoxy resin having an epoxy equivalent of 400 g/eq and a bromine content of 48.5% and a sulfur content of 14.8 were added. 8.4 g of 4,4'-diaminodiphenyldisulfide with a phosphorus content of 3.0% and 8.3 g of a general-purpose DOPO-modified epoxy resin having an epoxy equivalent of 300 g/eq were mixed to obtain a bromine content of 3 %, a flame retardant resin mixture having a sulfur content of 1% and a phosphorus content of 0.2%, dissolved in an appropriate amount of acetone, and further dissolved after adding 5.5 g of dicyandiamide and 0.1 g of 2-methylimidazole, according to well-known The method of producing a copper clad laminate is referred to as a copper clad laminate K. The performance test results of the clad copper clad K are shown in Table 1.

Example 11

100 g of liquid bisphenol A type epoxy resin having an epoxy equivalent of 186 g/eq, pentyl bisphenol A 1.9 g having a phenolic hydroxyl equivalent of 272 g/eq, a bromine content of 58.5%, and a benzene having a sulfur content of 45%. 1.2 g of dithiol and phenolic hydroxyl equivalent of 300.Og/eq, DOPO etherified bisphenol A 8.9 g of phosphorus content of 10.0% were mixed, and the bromine content was 1%, the sulfur content was 0.5%, and the phosphorus content was 0.8. % of the flame retardant resin mixture is dissolved by adding an appropriate amount of acetone, and after further adding 50.8 g of a phenolic hydroxyl equivalent of 105 g/eq of a novolak type phenolic resin and 0.1 g of 2-methylimidazole, a copper clad laminate is obtained according to a known method. This copper clad laminate is called a copper clad laminate L, and the performance test results of the clad copper clad L are shown in Table 2.

Comparative example 1

100 g of brominated bisphenol A type epoxy resin (calculated as solid) with bromine content of 20% and epoxy equivalent of 420 g/eq, 2.6 g of dicyandiamide and 0.1 g of 2-methylimidazole were added. After adding an appropriate amount of acetone to dissolve, a copper clad laminate is prepared according to a known method, and the copper clad laminate is referred to as a copper clad laminate M. The performance test results of the clad copper clad M are shown in Table 2.

Comparative example 2

A market-standard standard brominated bisphenol A epoxy resin of 16.7 g (solids) and an epoxy equivalent of 186 g/eq of liquid bisphenol A epoxy resin with a bromine content of 20% and an epoxy equivalent of 420 g/eq. After mixing 50 g, an epoxy resin composition having a bromine content of 5% was obtained, dissolved in an appropriate amount of acetone, and then fully dissolved by adding 32.4 g of a phenolic hydroxyl equivalent of 105 g/eq of a novolak type phenolic resin and 0.1 g of 2-methylimidazole. A copper clad laminate is prepared according to a known method, and the copper clad laminate is referred to as a copper clad laminate N. The performance test results of the clad copper clad N are shown in Table 2.

Comparative example 3

100 g of liquid bisphenol A type epoxy resin having an epoxy equivalent of 186 g/eq was taken, and 27.6 g of a brominated bisphenol A type epoxy resin having an epoxy equivalent of 400 g/eq and a bromine content of 48.5% was added, and after mixing, To a flame retardant resin mixture having a bromine content of 10.5%, dissolved in an appropriate amount of acetone, and further added with 6.4 g of dicyandiamide and 0.1 g of 2-methylimidazole, and after fully dissolving, the composition was prepared according to a general copper clad laminate. The program produces a standard copper clad board that meets the national standards, UL standards, etc. The copper clad plate is called a copper clad plate P, and the performance test results of the copper clad plate P are shown in Table 2.

Comparative example 4

100 g of liquid bisphenol A type epoxy resin having an epoxy equivalent of 186 g/eq was added, and 30.4 g of terephthalene with a sulfur content of 45% was added to obtain a flame retardant resin mixture having a sulfur content of 10.5%, and an appropriate amount was added. The acetone is dissolved, and 6.4 g of dicyandiamide and 0.1 g of 2-methylimidazole are further added, and after fully dissolving, the composition is used to prepare a standard copper clad board conforming to national standards, UL standards, etc. according to a general copper clad plate making procedure. This copper clad laminate is referred to as a copper clad laminate Q, and the performance test results of the clad copper clad Q are shown in Table 2.

Comparative Example 5

100 g of a liquid bisphenol A type epoxy resin having an epoxy equivalent of 186 g/eq was taken, and 29.3 g of a brominated bisphenol A type epoxy resin having an epoxy equivalent of 400 g/eq and a bromine content of 48.5% was added, and after mixing, A flame retardant resin mixture having a bromine content of 11% is dissolved in an appropriate amount of acetone, and after sufficiently dissolved by adding 6.7 g of dicyandiamide and 0.1 g of 2-methylimidazole, a copper clad laminate is obtained according to a known method. The copper plate is called the copper clad plate R, and the performance test results of the copper clad plate R are shown in Table 2.

Comparative Example 6

100 g of liquid bisphenol A type epoxy resin having an epoxy equivalent of 186 g/eq was taken, and 122 g of DOPO etherified bisphenol A having a phenolic hydroxyl equivalent of 300.0 g/eq and a phosphorus content of 10.0% was added to obtain a phosphorus content of 5.5. % of the flame retardant resin mixture is dissolved by adding an appropriate amount of acetone, and then fully dissolved after adding a phenolic hydroxyl equivalent of 105 g/eq of a novolak type phenolic resin (13.7 g) and 0.1 g of 2-methylimidazole. The method is to produce a copper clad laminate, and the copper clad laminate is referred to as a copper clad laminate S. The performance test results of the clad copper clad S are shown in Table 2.

Comparative Example 7

100 g of liquid bisphenol A epoxy resin having an epoxy equivalent of 186 g/eq, and 15.7 g of terephthalthiol having a sulfur content of 45% and tetrakis-(2,6-dimethylphenyl having a phosphorus content of 10.0%. After mixing 12.8 g of resorcinol diphosphate, a flame retardant resin mixture having a sulfur content of 5.5% and a phosphorus content of 1.0% was obtained, dissolved in an appropriate amount of acetone, and then 3.5 g of dicyandiamide and 0.1 g of 2 were added. After the methylimidazole was sufficiently dissolved, a copper clad laminate was obtained according to a known method, and the copper clad laminate was referred to as a copper clad laminate T. The performance test results of the clad copper clad T are shown in Table 2.

Comparative Example 8

100 g of liquid bisphenol A type epoxy resin having an epoxy equivalent of 186 g/eq, 2.86 g of terephthalene with a sulfur content of 45%, and tetrakis-(2,6-dimethylphenyl group having a phosphorus content of 10.0%. After mixing 154.5 g of resorcinol bisphosphate, a flame retardant resin mixture having a sulfur content of 0.5% and a phosphorus content of 6% was obtained, dissolved in an appropriate amount of acetone, and then 5.4 g of dicyandiamide and 0.1 g of 2 were added. After the methylimidazole is sufficiently dissolved, a copper clad laminate is obtained according to a known method, and the copper clad laminate is referred to as a copper clad laminate U. The performance test results of the copper clad laminate U are shown in Table 2.

It can be seen from the test results of Table 1 that the thermal decomposition temperature (5% weight loss) of the copper clad laminate prepared by using the flame retardant resin composition of the present invention can be as high as 353 ° C or more, and the peel strength can reach 1.8 kg / mm ^{2 .} Above, T-288>100 seconds, the heat resistance limit is 31 or more, the saturated water absorption rate can reach 0.35% or less, and the flammability (UL-94) reaches V-0 level.

When a commercially available standard brominated bisphenol A type epoxy resin having a bromine content of 20% and an epoxy equivalent of 420 g/eq was used without adding a sulfur-containing flame retardant (Comparative Example 1), although the bromine content was increased to 20%, the prepared copper clad laminate D also has a V-0 grade flame retardant performance, but the copper clad laminate has a low thermal decomposition temperature and is unstable, and the T-288 is only 15 seconds, and the heat resistance limit is only 5 times, the saturated water absorption rate is higher; and when the bromine bisphenol A type epoxy resin is used as a flame retardant with a bromine content of 20% and an epoxy equivalent of 420 g/eq, no sulfur-containing flame retardant is used. Also, when mixed with a liquid bisphenol A type epoxy resin having an epoxy equivalent of 186 g/eq as in Example 1, the bromine content was maintained at 10% in the epoxy resin composition (Comparative Example 2), The prepared copper clad laminate E has greatly reduced flame retardancy, and its heat resistance limit is only 8 times, the thermal decomposition temperature is low, the peel strength is low, and the saturated water absorption rate is high.

Compared with Example 1, when the sulfur-containing flame retardant was not used, the amount of the bromine-containing flame retardant was increased so that the bromine element content was equal to the sum of the bromine and sulfur element contents in Example 1 (Comparative Example 3), The obtained copper clad laminate has poor flame retardancy and other properties. Similarly, when the bromine-containing flame retardant is not used, the amount of the sulfur-containing flame retardant is increased so that the sulfur element content is equal to the bromine and sulfur element content in the first embodiment. At the same time (Comparative Example 4), the prepared copper clad laminate also exhibited poor flame retardancy and other properties, thus indicating that the bromine-containing flame retardant and the sulfur-containing flame retardant have flame retardancy in the present invention. Synergistic effect, and a small amount of sulfur element in the composition can be combined with a bromine-containing phenol compound and an epoxy resin to greatly improve the flame retardancy of the prepared copper clad plate. The phenolic compound containing bromine is used in the present invention. Its epoxy resin is used as a bromine-containing flame retardant, combined with a sulfur-containing flame retardant and a halogen-free epoxy resin, so that the prepared copper clad laminate has good comprehensive performance.

Compared with Example 4, when the phosphorus-containing flame retardant was not used, the amount of the bromine-containing flame retardant was increased so that the bromine element content was equal to the sum of the bromine and phosphorus element contents in Example 4 (Comparative Example 5), The obtained copper clad laminate was inferior in flame retardancy and other properties; compared with Example 7, when the bromine-containing flame retardant was not used, the amount of the phosphorus-containing flame retardant was increased so that the phosphorus element content was equal to that of Example 7. When the content of the bromine and phosphorus elements is the same (Comparative Example 6), the prepared copper clad plate also performs poorly in flame retardancy and other properties, thus indicating the bromine-containing flame retardant and the phosphorus-containing flame retardant in the present invention. The invention has synergistic effect on flame retardant performance, and the invention uses the bromine-containing phenolic compound and the epoxy resin thereof as the bromine-containing flame retardant, the phosphorus-containing flame retardant and the halogen-free epoxy resin, so that the prepared copper clad laminate has Good overall performance.

Compared with Example 8, when the bromine-containing flame retardant is not used, even if the sulfur element content in the composition is increased to be equal to the sum of the sulfur element and the bromine element content in Example 8 (Comparative Example 7) or in the composition The content of the phosphorus element was equal to the sum of the phosphorus element and the bromine element content in Example 8 (Comparative Example 8), and the obtained copper clad laminate was inferior in flame retardancy, and other properties such as heat resistance and water resistance were relatively poor.

Therefore, in the present invention, the bromine-containing flame retardant may be combined with a sulfur-containing flame retardant and/or a phosphorus-containing flame retardant to form a synergistic flame retardant, and the present invention uses a bromine-containing phenol compound and an epoxy resin thereof as a bromine-containing resistor. The flammable agent, combined with the sulfur-containing flame retardant and/or the phosphorus-containing flame retardant and the halogen-free epoxy resin, enables the prepared copper-clad laminate to have good comprehensive performance, and the invention can maintain the copper-clad laminate while reducing the bromine content. Flame retardant properties as well as heat resistance, water resistance and good mechanical properties.

The applicant has stated that the present invention is illustrative of the flame retardant resin composition, the thermosetting resin composition, the prepreg, and the composite metal substrate of the present invention, but the present invention is not limited to the above embodiment, that is, does not mean The invention must be implemented in accordance with the above embodiments. Own It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

Claims (10)

A flame retardant resin composition characterized in that the flame retardant resin composition comprises a bromine-containing flame retardant and a halogen-free epoxy resin; the bromine-containing flame retardant is a bromine-containing phenol compound and an epoxy resin thereof; The material also contains a sulfur-containing flame retardant and/or a phosphorus-containing flame retardant. The flame retardant resin composition according to claim 1, wherein the flame retardant resin composition has a bromine element content of 10% by weight or less, preferably 1-10% by weight; desirably, the flame retardant The content of sulfur element in the resin composition is 0.2% by weight or more, preferably 0.2 to 1%; desirably, the content of phosphorus element in the flame retardant resin composition is 0.2% by weight or more, preferably 0.2-2. %. The flame retardant resin composition as described in claim 1 or 2, wherein the bromine-containing flame retardant is a brominated phenol resin, a brominated phenolic epoxy resin, a brominated bisphenol A, or a brominated bisphenol. Any one or a combination of at least two of A derivative, brominated bisphenol A type epoxy resin, tetrabromobisphenol S, tetrabromobisphenol allyl ether, tribromophenol or pentabromophenol, preferably brominated Bisphenol A, brominated bisphenol A derivative or brominated bisphenol A type epoxy resin; desirably, the aforementioned sulfur-containing flame retardant is terephthalthiol and/or 4,4'-diaminodiphenyl Disulfide, ideally terephthalic phenol; ideally, the aforementioned phosphorus-containing flame retardant is DOPO etherified bisphenol A, DOPO modified epoxy resin, tris(2,6-dimethylphenyl)phosphine, Tetrakis-(2,6-dimethylphenyl)resorcinol diphosphate, resorcinol tetraphenyl diphosphate, triphenyl phosphate, bisphenol A bis(diphenyl phosphate), phosphazene Fuel, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphinophen-10-oxide, 10-(2,5-dihydroxy Naphthyl)-10-hydro-9-oxa-10-phosphinophen-10-oxide or 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide flame retardant Any one or a mixture of at least two. The flame retardant resin composition according to any one of claims 1 to 3, wherein the flame retardant resin composition may further comprise another flame retardant material; desirably, the other flame retardant material is an organic barrier Any one or a combination of at least two of a flammable agent, a chlorine-containing organic flame retardant, a nitrogen-containing organic flame retardant or an inorganic flame retardant; desirably, the aforementioned chlorine-containing organic flame retardant is tetrachlorophthalic acid Any one or a combination of at least two of octyl ester, chlorinic anhydride, chlorinic acid or tetrachlorobisphenol A; desirably, the aforementioned nitrogen-containing organic flame retardant is any of dicyandiamide, biuret or melamine One or a combination of at least two; desirably, the aforementioned inorganic flame retardant is any one or a combination of at least two of aluminum hydroxide, magnesium hydroxide, antimony trioxide or zinc borate. The flame retardant resin composition according to any one of claims 1 to 4, wherein the halogen-free epoxy resin is selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenol type. At least any one of phenolic epoxy resin, bisphenol A novolac epoxy resin, o-cresol novolac epoxy resin, dicyclopentadiene type epoxy resin, isocyanate type epoxy resin or biphenyl type epoxy resin A mixture of the two; desirably, the aforementioned halogen-free epoxy resin in the aforementioned flame retardant resin composition has a mass percentage of 70 to 90%. A thermosetting resin composition, characterized in that the thermosetting resin composition contains the flame retardant resin composition according to any one of claims 1 to 5. The thermosetting resin composition according to claim 6, wherein the thermosetting resin composition further comprises a curing agent; desirably, the curing agent is selected from the group consisting of dicyandiamide, phenolic resin, aromatic amine, acid anhydride, and active ester. Any one or a combination of at least two of a curing agent or an active phenolic curing agent; desirably, the thermosetting resin composition further includes a curing accelerator; desirably, the curing accelerator is an imidazole curing accelerator, and the organic phosphine is cured. Any one or a mixture of at least two of a promoter or a tertiary amine curing accelerator; desirably, the aforementioned imidazole compound is selected from the group consisting of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole , 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-12 Any one or a mixture of at least two of alkylimidazole or 1-cyanoethyl-2-methylimidazole is desirably 2-methylimidazole. A prepreg, characterized in that the thermosetting resin composition described in claim 6 or 7 is impregnated or coated on a substrate; desirably, the substrate may be a glass fiber substrate or a polyester substrate. , a polyimide substrate, a ceramic substrate or a carbon fiber substrate. A composite metal substrate characterized in that at least one prepreg as described in claim 8 of the patent application is sequentially coated with a metal layer, overlapped, and laminated; ideally, the material of the surface metallization layer is An alloy of aluminum, copper, iron and any combination thereof; ideally, the composite metal substrate is CEM-1 copper clad laminate, CEM-3 copper clad laminate, FR-4 copper clad laminate, FR-5 copper clad laminate, CEM-1 aluminum substrate, Any of CEM-3 aluminum substrate, FR-4 aluminum substrate or FR-5 aluminum substrate. A circuit board characterized by the surface processing circuit of the composite metal substrate described in claim 9 of the patent application.