KR20020060316A - Flame retardant epoxy resin composition of halogen free, prepreg containing it and brassfoil laminate - Google Patents

Abstract

PURPOSE: Provided are a non-halogen-based fire-retardant epoxy resin composition preventing the generation of toxic carcinogenic substances and the corrosiveness of metals, prepreg and a copper foil laminate containing the non-halogen-based fire-retardant epoxy resin composition. CONSTITUTION: The non-halogen-based fire-retardant epoxy resin composition comprises a bisphenol A type epoxy resin not containing bromine, a derivative of non-halogen-based aromatic phosphoric acid containing 2-8wt%(based on the total weight of the epoxy resin) of phosphorus, 10-50phr(based on the solid of the epoxy resin) of melamine cyanurate, 15-50phr(based on the solid of the epoxy resin) of a phenol novolac curing agent. The prepreg contains 40-50wt% of the non-halogen-based fire-retardant epoxy resin composition and the balance being glass fiber. And the copper foil laminate comprises 3-13 pieces of the prepreg and copper foil laminated on the both sides of the prepreg.

Description

Flame-retardant epoxy resin composition of halogen free, prepreg containing it and brassfoil laminate}

The present invention relates to a non-halogen flame-retardant epoxy resin composition and a prepreg and copper foil laminated plate containing the same. More specifically, the present invention is a non-halogen flame retardant epoxy resin composition comprising a bisphenol A epoxy resin, a non-halogen-based aromatic phosphate derivative, a melamine cyanurate, and a phenol novolac-based curing agent, and a prepreg and copper foil containing the same. It relates to a laminate.

Currently, there is a demand for higher safety for the environment and human body as well as flame retardancy for electric and electronic products around the world. In other words, in the case of electrical and electronic products, not only the flame retardancy is required but also the generation and fume of harmful gases during combustion and use should be low.

In general, a substrate made of glass epoxy is used as a printed wiring board for mounting electrical and electronic components. The flame-retardant copper foil laminated board using epoxy serves as an important element in manufacturing the epoxy flame-retardant copper laminated board used in this case (FR-4 Grades above) are required to be UL-94 V0 or above for their flame retardant performance.

In order to satisfy the flame retardant performance, a flame retardant is used to prepare a necessary resin composition, and conventional flame retardant epoxy resins are prepared by using tetrabromobisphenol-A (TBBA), which is a halogen flame retardant, when synthesizing an epoxy resin. The reaction is used, or TBBA is added to the epoxy resin to cure the epoxy resin. However, in the method using the halogen-based flame retardant, since bromine compounds such as hydrogen bromide, which are corrosive and harmful to metals, are generated during combustion and use, care should be taken in places where precise electronic equipment is installed, and it is difficult to decompose biologically. Aromatic bromine compounds, such as polybromine dibenzooxane, toxic carcinogens, such as dioxins and benzofuran, are limited in use.

Recently, in the case of phenolic copper clad laminates, a manufacturing method using a non-halogen-based flame retardant has been developed, and British Patent No. 1,112,139 and Japanese Patent Laid-Open Publication No. 90-269730 describe nitrogen compounds, phosphorus compounds and inorganic compounds as flame retardants. The composition which mix | blended these is described. Further, according to German Patent Publication No. 4,223,632, molding materials of latent reactive phenol-cured epoxy resins for giving flame retardance without using a halogen-based flame retardant are known. In order to solve the problems of combustion and use of halogen-based epoxy resins, a composition containing non-halogen-based flame retardants such as phosphorus compounds, nitrogen compounds and inorganic compounds has been developed as described above, but non-halogen flame-retardant additives are also used for curing epoxy resins. There was a problem of adversely affecting or lowering the moisture resistance or impregnation of the cured composition.

SUMMARY OF THE INVENTION An object of the present invention is to provide a non-halogen flame-retardant epoxy resin composition, a pre-flag and a copper-clad laminate containing the same, which exhibits good flame retardancy by using a non-halogen-based flame retardant and solves problems such as generation of toxic carcinogens and metal corrosion. To provide.

Non-halogen flame retardant epoxy resin composition according to the present invention

(A) bisphenol A epoxy resin (bromine free),

(B) a non-halogen aromatic phosphate derivative in an amount of 2 to 8% by weight based on the total amount of epoxy resin,

(C) melamine cyanurate 10 to 50 phr (part per hundred resin) based on epoxy resin (solid content), and

(D) phenol novolak-based curing agent is characterized in that it comprises 15 to 50 phr based on the epoxy resin (solid content).

Prepreg according to the invention is characterized in that it comprises a glass fiber in the remaining amount and 40 to 50% by weight of the non-halogen flame-retardant epoxy resin composition.

The copper clad laminate according to the present invention is characterized in that the copper foil is laminated on both sides of 3 to 13 sheets of prepreg.

Hereinafter, specific embodiments of the present invention will be described in detail.

Non-halogen flame retardant epoxy resin composition according to the present invention

(A) bisphenol A epoxy resin (bromine free),

(B) a non-halogen aromatic phosphate derivative in an amount of 2 to 8% by weight based on the total amount of epoxy resin,

(C) melamine cyanurate 10 to 50 phr based on the epoxy resin (solid content), and

(D) phenol novolak-based curing agent is characterized in that it comprises 15 to 50 phr based on the epoxy resin (solid content).

The bisphenol A epoxy resin is characterized in that it has an epoxy equivalent of 200 to 1500 as a basic component of the resin composition.

The non-halogen aromatic phosphate derivative is characterized in that it has a structure of formula (1). This material takes oxygen and hydrogen away from the polymer to form phosphoric acid, metaphosphoric acid, and polymetaphosphate, forming an acid film on the surface of the plastic to block heat and oxygen along with the char. In case of using aromatic phosphate derivative alone, more amount should be used, but in case of using excessive amount, it should be noted that it shows the result of deteriorating the properties of copper clad laminate, and in combination with melamine cyanurate, it is a flame retardant synergistic effect. Flame retardant effect can be obtained. Suitable amounts may vary depending on the amount of melamine cyanurate, but the amount of phosphorus is 2 to 8% by weight, preferably 3 to 6% by weight, based on the total amount of epoxy resin. Since phosphorus content varies depending on the type of aromatic phosphoric acid derivative, the amount of phosphorus used is calculated based on the phosphorus content in the entire epoxy resin according to the following formula.

Phosphorus (P) content (% by weight) = (The amount of aromatic phosphoric acid derivative X phosphorus content of aromatic phosphoric acid derivative) / (Epoxy resin amount + Aromatic phosphoric acid derivative amount + Hardener amount used) X 100

Wherein R is H or CH ₂ CH ₂ OH.

The melamine cyanurate is a compound having the structure of Formula 2, and has the effect of preventing not only flame retardant effect but also lowering of heat resistance. This material has a flame retardant effect on its own, but synergistic effect of phosphorus and nitrogen when combined with phosphorus-based flame retardants. Therefore, when melamine cyanurate is used in combination with a phosphorus-based flame retardant in the manufacture of the laminate, the laminate exhibits excellent flame retardant effect and heat resistance. The suitable amount is 10 to 50 phr based on the epoxy resin (solid content), and the amount of use is also related to the amount of phosphorus flame retardant, so the optimum amount of flame retardant and physical properties can be obtained only by adjusting the amount according to the amount of phosphorus flame retardant. .

The phenol novolac-based curing agent is used for curing epoxy resin, and the dicyanamide or amine curing agent generally used for copper clad laminates is excellent in curing properties compared with being hindered by the curing reaction under the influence of aromatic phosphate derivatives. Have. The usage-amount of a phenol novolak-type hardening | curing agent is 15-50 phr based on epoxy resin (solid content), Preferably it is 20-40 phr. In case of using 15 phr or less, the physical property is not completely cured, and the physical properties are remarkably lowered. In case of using 50 phr or more, the control of the rate of curing reaction is not only a problem, but the properties of the epoxy resin are not well represented. There is a problem that the physical properties are inadequate.

In addition to the above components, a flame retardant aid may be added. The flame retardant aid is a compound which supplements and catalyzes the flame retardancy of the phosphorus-based flame retardant and melamine cyanurate and further improves the flame retardancy, and it is preferable to use a triazine compound containing an epoxy group and 0 to 2 based on the epoxy resin (solid content). phr, preferably 0.5 to 1 phr. In general, when the phosphorus-based flame retardant and melamine cyanurate are sufficiently used, it is not necessary to use a flame retardant aid, but when using the flame retardant aid, it is preferable to use it because it obtains an additional effect of improving physical properties and reducing the amount of phosphorus-based flame retardant.

Prepreg according to the invention is characterized in that it comprises a glass fiber in the remaining amount and 40 to 50% by weight of the non-halogen flame-retardant epoxy resin composition.

The copper clad laminate according to the present invention is characterized in that 3 to 13 sheets of prepreg and copper foil are laminated on both surfaces thereof.

The non-halogen flame-retardant epoxy resin composition and the prepreg and copper-clad laminate containing the same according to the present invention are caused by toxic carcinogens such as dioxin and benzofuran generated by using a conventional halogen-based flame retardant and hydrogen bromide generated during combustion. It has solved the problems such as harmfulness and metal corrosion, and it has the effect of increasing the flame retardant by using the nitrogen-based melamine cyanurate in parallel, and the properties and characteristics of the copper clad laminates are equivalent to those of the copper clad laminates. Can be obtained. In addition, by applying a phenol novolak-based curing agent, it is possible to prevent a reduction in the curing reaction generated when using an existing imide-based or amine-based curing agent and to obtain a product having excellent physical properties such as heat resistance.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described.

The following examples are intended to illustrate the invention and should not be understood as limiting the scope of the invention.

Example 1

Into a 500 ml flask, 30 g of a phenol novolac curing agent (HF-4, manufactured by Nippon Dodo Chemical), add 60 ml of acetone to dissolve, and add 0.2 g of epoxy-containing triazine (Japan Japan Inks Co., Ltd.), a reactive flame-retardant aid, completely. Solution A was prepared by stirring until dissolved and mixed. 125 g of YDB11A80 (Korea Kukdo Chemical Co., Ltd., 80% resin content), a nonflammable resin of epoxy equivalent 400, was added to Solution A, stirred until thoroughly mixed, and phosphorus content of 14.5% by weight of 3-hydroxyphenyl phosphinyl propanoic acid Hiretar 30 g of -205 (Kolon Korea Co., Ltd.) and 31 g of melamine cyanurate (Mitsubishi Chemical Co., Ltd.) were added thereto, followed by stirring until complete mixing to prepare a resin composition.

The resin composition thus prepared was impregnated into glass fiber and then hot-air dried to prepare a prepreg having a resin content of 43% by weight.

Eight pieces of this prepreg were laminated, copper foil having a thickness of 18 um on both sides, and laminated, and then heated and pressed for 90 minutes at a temperature of 170 ° C. and 40 kg / cm ² using a press to prepare a copper foil laminated plate having a thickness of 1.6 mm. It was.

The lead heat resistance of the manufactured copper clad laminate was measured as the time to withstand in a 288 ° C lead bath, that is, the time taken for the copper clad laminate to explode. Flame retardancy was measured by UL94 test method, which is a standard method for evaluating flame retardancy divided into V ₀ , V ₁ and V ₂ grades by vertical combustion test. The results are shown in Table 1.

Example 2

Instead of Hiretar-205, it was carried out in the same manner as in Example 1, except that 43 g of phosphorus content of 3-ethyleneglyoxyphenylphosphinyl phosphonic acid ethylene glycol ester Hiretar-205EG (Kolon Korea) was used. . The results are shown in Table 1.

Example 3

The same procedure as in Example 1 was carried out except that 38 g of Hiretar-205 and 40 g of melamine cyanurate were used without using an epoxy-containing triazine. The results are shown in Table 1.

Comparative Example 1

The same procedure as in Example 1 was carried out except that Hiretar-205 was not used at all. The results are shown in Table 1.

Comparative Example 2

The same procedure as in Example 1 was conducted except that no melamine cyanurate was used. The results are shown in Table 1.

Comparative Example 3

Dicyandiamide was used in place of the phenol novolac curing agent in the same manner as in Example 1, except that 2.5 phr of epoxy resin (solid content) was used. The results are shown in Table 1.

Comparative Example 4

After diluting 2.5 g of dicyanodiamide into 20 g of dimethylformamide, completely dissolving, 0.15 g of 2-methylimidazole and 15 g of methyl serosolve were added thereto, and stirred until completely dissolved and mixed to prepare Solution B. 125 g of YDB424A80 (Korea Kukdo Chemical Co., Bromine content 18-22 wt%) of epoxy equivalent 450-500 was added to Solution B, and 0.13 g of 2-ethyl-4-methylimidazole, a curing accelerator, was dissolved in acetone and completely added. After the mixture was stirred, acetone was further added to prepare a resin composition having a specific gravity of 1.10.

Since the process was carried out in the same manner as in Example 1. The results are shown in Table 1.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 color Colorless Colorless Colorless Colorless Colorless Colorless Colorless Lead heat resistance (S / B, sec) 210 160 185 260 190 Uncured 180 Flame Retardant (UL94) V ₀ V ₀ V ₀ HB V ₂ Uncured V ₀ ※ V ₀ is best for flame retardancy, and flame retardancy is inferior to V ₁ , V ₂ , HB and UL V ₀ for flame retardant electrical and electronic materials.

As shown in Table 1, the copper-clad laminate of the example containing the non-halogen flame-retardant epoxy resin composition according to the present invention has superior lead heat resistance and flame retardancy compared to the copper-clad laminate of the comparative example containing a conventional halogen-based flame-retardant epoxy resin composition. It can be seen that.

Therefore, according to the present invention, a non-halogen flame-retardant epoxy resin composition and a prepreg and copper-clad laminate containing the same, which exhibit good flame retardancy by using a non-halogen-based flame retardant and solve the problems of generation of toxic carcinogens and metal corrosiveness of the prior art. There is an effect that can provide.

Although the present invention has been described in detail only with respect to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, and such modifications and modifications are within the scope of the appended claims.

Claims (5)

(A) bisphenol A epoxy resin (bromine free), (B) a non-halogen aromatic phosphate derivative in an amount of 2 to 8% by weight based on the total amount of epoxy resin, (C) melamine cyanurate 10 to 50 phr based on the epoxy resin (solid content), and (D) Non-halogen flame-retardant epoxy resin composition characterized in that the phenol novolak-based curing agent comprises 15 to 50 phr based on the epoxy resin (solid content). The method of claim 1, Non-halogen flame retardant epoxy resin composition, characterized in that the bisphenol A epoxy resin has an epoxy equivalent of 200 to 1500. The method of claim 1, Non-halogen flame-retardant epoxy resin composition, characterized in that the non-halogen aromatic phosphate derivative has a structure of formula (1). Formula 1 Wherein R is H or CH ₂ CH ₂ OH. A non-halogen flame retardant epoxy resin composition according to any one of claims 1 to 3, and prepreg, characterized in that it comprises a glass fiber in a balance of 50 to 50% by weight. The copper clad laminated board characterized by laminating | stacking copper foil on 3 to 13 sheets of the prepreg of Claim 4, and both surfaces.