KR100197946B1 - Epoxy-copper laminated resin compositions having excellent flame-retardant and heat-resistance - Google Patents

Abstract

The present invention relates to a resin composition for use as a multilayer electronic circuit board and a halogen-free flame retardant epoxy copper-clad laminate.

(A) 0.1 to 20 g of (C) a dicyanoamide curing agent in an amount sufficient to give a total phosphorus content of 3 to 30% in the epoxy resin (B) per 100 g of the bromine-free trifunctional epoxy resin (D) 0.01 to 3 g of an amidazole-based curing accelerator, (E) 0 to 200 g of an inorganic flame-retardant auxiliary, and (F) 0.1 to 3 wt% of a coupling agent based on the weight of the inorganic flame-

The equivalent weight of the epoxy resin is 200 to 700, and the silver has the structure of the general formula (II).

The resin composition of the present invention uses a phosphorus-based flame retardant instead of the conventional halogen-based flame retardant to solve the problems caused by gas generated during combustion and metal corrosion, and improves the heat resistance and flame retardancy of the laminate.

Description

Resin composition for an epoxy copper clad laminate excellent in flame retardancy and heat resistance

The present invention relates to a resin composition for an epoxy copper-clad laminate which is used as a multilayer electronic circuit board and is excellent in flame retardancy and heat resistance, which is free from halogen. In general, flame retardancy is an important factor in producing a flame-retardant epoxy copper-clad laminate. The flame-retardant copper-clad laminate using epoxy is required to have UL-94VO grade in its flame retardant performance.

In order to satisfy such a flame retardant performance, a resin composition is prepared using a flame retardant. The conventional flame-retardant epoxy resin is prepared by reacting Tetrabromobisphenol A (hereinafter referred to as TBBA) at the time of epoxy resin synthesis , And secondly, TBBA is added to an epoxy resin and then the epoxy resin is cured at the time of curing.

That is, as a flame retardant imparting flame retardancy in the production of a copper-clad laminate, a phenolic copper-clad laminate (P) system and TBBA are mixed, while in the case of a flame-retardant epoxy copper-clad laminate, only TBBA or a halogen-based flame retardant is used.

When such a flame retardant epoxy copper-clad laminate is produced by using such a halogen-based flame retardant, toxic carcinogens such as polyhalogenated aromatic dioxin or dibenzofuran are generated when the flame retardant is burned. In particular, in the case of a polybrominated flame retardant, toxic carcinogens such as decarbromophenyldioxide and octabromophenylether are generated. In addition, halogen compounds are harmful to the human body due to gases such as HBr and HCl generated during combustion, and metal is corroded. Therefore, there is a problem in that it is necessary to pay attention to use in a place where precision electronic equipment is installed. In addition, the thin core copper laminate used as the core material used for the laminate multi-layered circuit board is formed through a plurality of processes in which a thermal change is severe to form a multi-layer circuit board. The thin copper- And requires a high glass transition temperature as its characteristic value. When the heat resistance is insufficient, the operation laminated board is lifted due to hot thermal shock such as lead treatment (260 ° C or more) in manufacturing a multilayer printed circuit board, and a chip is mounted after completion of the circuit due to thermal expansion due to thermal change There arises a problem that the hole becomes incapable of being used.

An object of the present invention is to provide a flame retardant epoxy copper-clad laminate for multilayer circuit boards having high heat resistance while eliminating harmfulness of a halogen-based compound by using an inorganic flame retardant without using a halogen- To an epoxy resin composition.

The present invention will be described in more detail.

The epoxy resin composition of the present invention contains, as essential components, a bromine-free trifunctional epoxy resin, a curing agent and a curing accelerator, and optionally contains an inorganic flame-retardant auxiliary agent and a coupling agent.

Bromine-free trifunctional epoxy resin Having the same structure as the general formula (I), the epoxy equivalent is 200 to 700, which is a basic composition of the resin composition.

Is a substance having the structure of the general formula (II) and has a flame retarding mechanism of the general formula (III).

It is known that there is a difficulty in commercialization because there is a merit that it can obtain a sufficient flame retardant effect because it is composed of a small amount of silver phosphorus itself, but it has a problem of ignition on the market, deterioration of resin characteristics under high temperature and high humidity, Therefore, it is better to use a product that is coated with a resin or the like to enhance the stability rather than using the product itself.

The amount of phosphorus used is 3 to 30% of phosphorus content in the epoxy resin. The phosphorus content of epoxy resin is different according to the kind of phosphorus. Therefore, the amount of phosphorus is calculated based on the phosphorus content of the whole resin. In addition, it is necessary to use a larger amount in case of using alone, and since it has a flame-retarding effect when it is used in combination with an inorganic flame-retardant aid, the same flame-retarding effect can be obtained even if a smaller amount is used.

The proper amount to be used is 5 to 20% based on the phosphorus content of the resin when used alone, and when the inorganic flame-retardant aid is used in combination with the inorganic flame-retardant aid, there is a difference depending on the amount of the inorganic- It is suitable to use 3 to 15%.

Dicyanodiamide is used as the hardening agent, and the dosage is preferably 0.5 to 20 PHR. Here, PHR means the number of grams (g) of the curing agent added per 100 g of the epoxy resin. PHR used in the future indicates the number of grams (g) of various compounds added per 100 g of epoxy. When the amount of the curing agent is less than 0.5 PHR, the amount of the curing agent is small and the curing agent is not fully cured. Therefore, the physical properties of the curing agent are remarkably low. When 20 PHR or more is used, the uncured agent remains as a monomer even after the curing is completed. There is a disadvantage that the result is deteriorated.

As the curing accelerator, 2-methylimidazole, 2-ethyl-4-methyl imidazole and benzimidazole are used singly or in combination as the curing accelerator for the imidazole system, the amount of which is 0.01 to 3.0 PHR per 100 g of the resin, The amount is adjusted according to the properties of the prepreg. Since this is a curing accelerator for accelerating the reaction, it can be controlled according to the production conditions of the copper-clad laminate, and it is difficult to control the reaction when the excess amount is used, and the cost is increased by hindering the reaction of the curing agent.

As the inorganic flame retardant auxiliary, magnesium hydroxide (Mg (OH) ₂ ), aluminum hydroxide (Al (OH) ₂ ), antimony trioxide (Sb ₂ O ₃ ) and antimony pentoxide (Sb ₂ O ₅ ) When used in combination with a metal hydroxide such as magnesium hydroxide or aluminum hydroxide, exhibits an excellent flame retarding effect.

The amount of use is 0 ~ 200 PHR compared with 100g of epoxy resin. It is also related to the usage amount of epoxy resin. Therefore, it is preferable to use inorganic flame retarding adjuvant in large quantity when using a small amount of inorganic flame retarding adjuvant.

When varnish is produced by using such an inorganic flame-retardant aid and impregnated into glass fiber or glass non-woven fabric, the inorganic flame retardant itself is not well dispersed, and since a precipitate is formed, it is coated with a coupling agent in advance It is preferable to use it afterwards.

Titanate-based and silane-based compounds are used as the coupling agent, and the amount thereof is 0.1 to 3% by weight based on the weight of the inorganic flame-retardant aid. If the amount is too small, the inorganic flame-retardant aid may not be completely coated to cause a problem of dispersion, and therefore, there is a problem that a precipitate is formed. In an excessive use, the monomer itself remains as a monomeric material and causes a rise in cost.

A suitable amount is 0.3 to 1.5 wt% of the weight of the inorganic flame retardant.

The resin composition of the present invention has a problem that toxic carcinogens such as polyhalogenated aromatic dioxin or dibenzofuran are generated when the flame-retardant epoxy copper-clad laminate uses a halogen-based flame retardant, As a flame retardant, toxic carcinogens such as decabromopheneyldioxide and octabromopheneylether are generated. In addition, harmfulness and metal corrosion due to gases such as HBr and HCl generated when the halogen compound is burned And a non-halogen flame retardant is used. In addition, it is possible to solve the problem of dispersion occurring when using such inorganic flame retardant and flame retardant adjuvant.

The present invention uses a halogen-free flame retardant in combination with an inorganic flame-retarding auxiliary such as a metal hydroxide to obtain a synergistic effect of flame retardancy and obtain excellent flame retardancy even by use of a small amount of flame retardant. In particular, when used in combination with magnesium hydroxide, It shows excellent effect.

The following examples illustrate the effects of the present invention and do not define the scope of the present invention.

[Example 1]

0.5 g of a titanate coupling agent KR38S (manufactured by Ajinomoto Co., Ltd.) was added to a 500 ml flask, and 50 ml of acetone was added to dissolve it. Then, 50 g of magnesium hydroxide was added thereto and stirred until complete mixing to prepare Solution 1 . 2.5 g of anodiamide was added to 20 g of N, N'-dimethylformamide and completely dissolved. Then, 0.15 g of 2-methylimidazole and 15 g of methylcellosol were added and stirred to complete dissolution to prepare solution 2 do.

100 g of VG3101M80 trifunctional resin (epoxy equivalent 210, manufactured by Samjung Petrochemical Co., Ltd.) was added to the solution 2 and stirred until the mixture was completely mixed. Thereafter, the solution 1 and 120 UF of RINKA coated with a synthetic resin Amount: 75%), and the mixture was stirred until thoroughly mixed to prepare a resin composition.

The resin composition thus prepared is impregnated with glass fiber and then subjected to hot air drying to prepare a prepreg having a resin content of 43% by weight.

8 sheets of these prepregs were laminated and a copper foil having a thickness of 18 um was placed on both sides and laminated and then heated and pressed under a temperature and pressure of 170 캜 and 40 kg / cm 2 for 90 minutes using a press to produce a copper clad laminate having a thickness of 1.6 mm .

The solder blister was measured by the time taken for the copper-clad laminate to withstand the 288 ° C lead time, that is, the time taken for the copper-clad laminate to blow up. Flame retardancy was measured by removing the operation by the etching method, and the remaining laminate was tested by the vertical flame- Respectively.

The Tg was measured in the range of 30 to 270 占 폚 while the temperature was raised at a rate of 20 占 폚 / min using DSC-7 manufactured by Perkin-Elmer. The measurement results are shown in Table 1.

[Example 2]

A copper alloy laminate was produced under the same conditions as in Example 1 except that the same amount of aluminum hydroxide was used in place of the magnesium hydroxide in Solution 1 of Example 1, and the lead heat resistance and flame retardancy were measured. The measurement results are shown in Table 1.

[Example 3]

A copper-clad laminate was produced under the same conditions as in Example 1, except that the magnesium hydroxide and titanate coupling agent of the solution 1 in Example 1 were not used but increased to 14.2 g, and the lead heat resistance, flame retardancy and Tg Respectively. The measurement results are shown in Table 1.

[Example 4]

Except that 11.1 g of RINKA FR 280A (a product of Japanese Pharmacopoeia, phosphorus content 45 to 55%), which is a blended product of 120 UF of RINKA and Titanium dioxide of Example 1, 1, the lead heat resistance, flame retardancy and Tg were measured. The measurement results are shown in Table 1.

[Comparative Example 1]

Example 1 Copper-clad laminate was produced under the same conditions as in Example 1, except that no intermediate was used at all, and lead heat resistance and flame retardancy were measured. The measurement results are shown in Table 1.

[Comparative Example 2]

Copper clad laminate was produced under the same conditions as in Example 1, except that the magnesium hydroxide and coupling agent of Example 1 and Solution 1 were not used, and the lead heat resistance and flame retardancy were measured. The measurement results are shown in Table 1.

[Comparative Example 3]

Except that the epoxy resin of Example 1 and the magnesium hydroxide and coupling agent of Solution 1 were not used, the same amount of YDB424A80 (epoxy equivalent: 400, Kukdo Chemical Co., Ltd.), which is a conventional brominated flame retardant resin, was used in the same manner as in Example 1 And the lead heat resistance and flame retardancy were measured. The measurement results are shown in Table 1.

[Comparative Example 4]

A copper clad laminate was produced under the same conditions as in Example 1, except that the same amount of non-burnable epoxy resin YD011A80 (epoxy equivalent: 400, Kukdo Chemical Co., Ltd.) was used instead of the trifunctional epoxy resin of Example 1, And Tg were measured. The measurement results are shown in Table 1.

Claims (7)

0.5 to 20 g of a dicyanoamide curing agent and 0.01 to 3 g of an amidazole curing accelerator per 100 g of the bromine-free trifunctional epoxy resin in an amount such that the total phosphorus content in the epoxy resin can be 3 to 30% , 0 to 200 g of an inorganic flame retardant auxiliary agent, and 0.1 to 3% by weight of a coupling agent based on the weight of the inorganic flame retardant auxiliary agent. The resin composition for an epoxy copper-clad laminate according to claim 1, wherein the trifunctional epoxy resin has an epoxy equivalent of 200 to 700, and is excellent in flame retardancy and heat resistance. The resin composition for an epoxy copper-clad laminate according to claim 1, wherein the trifunctional epoxy resin has a structure represented by the general formula (I), which is excellent in flame retardancy and heat resistance. The resin composition for an epoxy copper-clad laminate according to any one of claims 1 to 3, wherein the resin has a structure represented by formula (II). The resin composition for epoxy laminate according to claim 1, wherein the curing accelerator is selected from 2-methylimidazole, 2-ethyl-4-methylimidazole and benzimidazole. The resin composition according to claim 1, wherein the inorganic flame-retardant auxiliary is at least one compound selected from the group consisting of magnesium hydroxide, aluminum hydroxide, antimony trioxide and antimony pentoxide. The resin composition for an epoxy copper-clad laminate according to claim 1, wherein the coupling agent is a titanate compound or a silane compound, and is excellent in flame retardancy and heat resistance.