KR19980030464A - Resin composition for flame-retardant epoxy copper foil laminate - Google Patents

Abstract

The present invention is used as a multilayer electronic circuit board, and relates to a resin composition for an epoxy copper foil laminate having excellent flame retardancy and heat resistance.

The resin composition of the present invention is (A) a bromine-free bisphenol A-type epoxy resin (B) an amount of an amount of 2 to 20% of the total phosphorus content in the epoxy resin (B) 0.5 to 20 g of a dicyanoamide curing agent And (D) 0.01 to 3 g of amidazole-based curing accelerator, (E) 0 to 150 g of inorganic flame retardant (F) 1 to 10 g of flame retardant catalyst (G), and 0.1 to 3% by weight of coupling agent relative to the weight of inorganic flame retardant. .

The epoxy equivalent of an epoxy resin is 300-1,500, and the red has a structure of general formula (I).

The resin composition of the present invention improves the heat resistance and flame retardancy of the laminate while solving problems such as corrosion and metal corrosion caused by the gas generated during combustion by using phosphorus-based flame retardant instead of the halogen-based flame retardant.

Description

Resin Composition for Flame Retardant Epoxy Copper Clad Laminates

The present invention relates to a resin composition for a flame-retardant epoxy copper foil laminate that is used as a multilayer electronic circuit board and does not contain halogen.

In general, the flame retardancy is an important factor in the production of flame-retardant epoxy copper foil laminate plate, the flame-retardant copper foil laminate using epoxy requires UL-94VO grade for its flame retardant performance.

In order to satisfy the flame retardant performance, a resin composition is prepared using a flame retardant. Existing flame retardant epoxy resins are prepared by first reacting tetrabromobisphenol-A (hereinafter referred to as TBBA) when synthesizing an epoxy resin. Second, TBBA is added to the epoxy resin, and then the epoxy resin is cured in the same manner as curing.

In other words, phosphorus (P) -based and TBBA are used as a flame retardant for imparting flame retardancy in the production of copper foil laminate, whereas TBBA, that is, halogen-based flame retardant, is used in the case of flame-retardant epoxy copper foil laminate.

When the flame-retardant epoxy copper foil laminate is manufactured using such a halogen-based flame retardant, toxic carcinogens such as polyhalogenate aromatic dioxin or dibenzofuran are generated during combustion of the flame retardant.

Particularly in the case of polybrominated flame retardants, there is a problem that toxic carcinogens such as decarbromo phenyldoxide and octabromophenylether are generated. In addition, the halogen-based compound is harmful to the human body due to the gas such as HBr and HCl generated during combustion, there is a problem that must be used in places where precision electronic equipment is installed due to the problem of corrosion of metal.

The present invention provides an epoxy resin composition for a flame-retardant epoxy copper foil laminated plate which does not use such a halogen-based flame retardant but removes the harmfulness of a halogen-based compound by using an inorganic flame retardant.

The present invention will be described in more detail.

The epoxy resin composition of the present invention is composed of a bromine-free bisphenol A epoxy resin, an inorganic flame retardant aid, a flame retardant catalyst, a coupling agent, a curing agent, and a curing accelerator.

The bromine-containing bisphenol A epoxy resin has an epoxy equivalent of 300 to 1,500 and is a basic composition of the resin composition.

An enemy is a substance having the structure of general formula (I) and has a flame retardant mechanism of general formula (II).

It is known that the enemy has the advantage of being able to obtain sufficient flame retardant effect because of its small amount, whereas commercially available enemies are known to have problems of ignition, deterioration of resin properties under high temperature and high humidity, and commercial difficulties. Therefore, it is better to use a product having improved stability by coating with resin, rather than using a product of the enemy itself.

The amount of phosphorus used is 2 ~ 20% phosphorus content in epoxy resin. Since phosphorus content varies according to the type of phosphorus, the amount of phosphorus is calculated and used based on the phosphorus content of the whole resin. In addition, when using the enemy alone, a larger amount must be used, and when used in combination with an inorganic flame retardant aid, a flame retardant synergistic effect can be obtained.

Suitable amount is 5 ~ 20% based on phosphorus content in resin when used alone, and it depends on the amount of inorganic flame retardant and flame retardant catalyst when used in combination with inorganic flame retardant and flame retardant catalyst. It is suitable to use 2 to 10% based on the phosphorus content of.

Inorganic flame retardant aids may be used alone or in combination of 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 metal hydroxides such as magnesium hydroxide or aluminum hydroxide shows excellent flame retardant effect.

As for the usage-amount, 0-150 PHR is suitable with respect to 100 g of epoxy resins. Here, PHR means the number of grams (g) of the inorganic flame retardant adjuvant added per 100 g of epoxy resin. PHR to be used in the future indicates the number of grams (g) of addition of various compounds per 100 g of epoxy. The amount of inorganic flame retardant aid is also related to the amount of use of the enemy. Therefore, it is preferable to use a large amount of inorganic flame retardant adjuvant when using a small amount of the enemy, and a small amount of inorganic flame retardant aid when using a large amount of the enemy.

In addition, since the flame retardant performance is greatly improved when the flame retardant catalyst is used, a suitable amount of the inorganic flame retardant aid is preferably 20 to 70 PHR compared to 100 g of the epoxy resin.

When the varnish is manufactured using such inorganic flame retardant aids and impregnated with glass fiber or glass nonwoven fabric, inorganic flame retardant itself is not well dispersed and precipitates are formed so that it is pre-coated with a coupling agent. It is preferable to use after.

The flame retardant catalyst is one of the characteristic conditions of the present invention and shows a feature that greatly improves the flame retardant performance of the flame retardant system in a small amount.

Therefore, by reducing the amount of the flame retardant and the flame retardant aid, it is possible to suppress the deterioration of physical properties such as heat resistance of the laminate itself due to the excessive use of the flame retardant and the flame retardant aid.

Flame retardant catalysts used include nickel compounds such as nickel (II) oxide, nickel (III) oxide, bis (8-hydroxyquinylino) nickel (II) and bis (acetylacetonate) nickel (II), ferrocene And magnesium borate (Magnesium borate) is used, but in the case of nickel compound is a heavy metal material, it is recommended to use ferrocene or magnesium borate. The amount used is 1 to 10 PHR compared to 100 g of epoxy resin, but the amount may be increased or decreased depending on the composition of the flame retardant system, and the suitable amount is 2 to 6 PHR in the present invention.

The coupling agent uses titanate-based and silane-based compounds, and the amount of the coupling agent is 0.1 to 3% by weight based on the weight of the inorganic flame retardant adjuvant.

If the amount is too small, the inorganic flame retardant aid is not completely coated, so there is a problem in dispersion, and thus there is a problem in that a precipitate is formed, and when used in excess, it becomes a monomer material as well as a cost increase factor.

Suitable amount is 0.3 to 1.5% by weight of inorganic flame retardant.

The curing agent is dicyanoodiamide (Dicyanodiamide) is used is suitable for 0.5 to 20 PHR. When using less than 0.5 PHR, the amount of hardening agent is small, so it is not completely hardened. Therefore, when using more than 20 PHR, the uncured agent remains as a counterpart of monomer even after curing is completed. There is a disadvantage in that the result is deteriorated.

The curing accelerator is used alone or in combination of imidazole-based curing accelerators 2-methylimidazole, 2-ethyl-4-methylimidazole and benzimidazole, the amount of use is 0.01 to 3.0 PHR per 100g resin, Adjust the amount according to the physical properties of the prepreg. Since it is a curing accelerator for promoting the reaction, it can be adjusted according to the manufacturing conditions of the copper foil laminate, and when excessively used, it is difficult to control the reaction, and the cost is increased by preventing the reaction of the curing agent.

The resin composition of the present invention is a conventional flame-retardant epoxy copper foil laminate is a problem that occurs when toxic carcinogens such as polyhalogenated aromatic dioxin or dibenzofuran when the halogen-based flame retardant is used, especially in the polybrominated flame retardant Toxic carcinogens such as decabromopheneyldioxide and octabromophenylether are generated, and also problems such as harmfulness and metal corrosion due to gas such as HBr and HCl generated during the combustion of halogen-based compounds. It is characterized by using a non-halogen-based flame retardant as a solution, and also can solve the dispersion problems such as when using the inorganic flame retardant and flame retardant aids.

The present invention has a synergistic effect of flame retardancy by using non-halogen flame retardant in combination with inorganic flame retardant aids such as metal hydroxide, so that even a small amount of flame retardant can be used to obtain excellent flame retardancy without changing the physical properties of the copper foil laminate, especially when used in combination with magnesium hydroxide Shows an excellent effect of increasing lead heat resistance.

In addition, the main feature of the present invention is to significantly increase the flame retardant effect by using a flame retardant catalyst to significantly reduce the amount of the use of inorganic and inorganic flame retardant aids to suppress the deterioration of the physical properties of the laminated board as well as to reduce the cost have.

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

Example 1

5 g of a titanate coupling agent KR38S (manufactured by Ajinomoto Co., Ltd.) was added to a 500 ml flask, 500 ml of acetone was added thereto, dissolved therein, and 300 g of magnesium hydroxide was added thereto, followed by stirring until complete mixing. Solution 1 was prepared.

25 g of dicyanodiamide was added to 200 g of dimethylformamide (N, N'-Dimethylformamide) and completely dissolved. Then, 1.5 g of 2-methylimidazole and 150 g of methyl cersolve were added thereto, followed by stirring to completely dissolve it. Manufacture.

1000 g of epoxy resin YDB011A80 (Epoxy equivalent 400, non-flammable resin, Kukdo Chemical) was added to Solution 2, and stirred until completely mixed. Then, 30 g of magnesium borate, a flame retardant catalyst, solution 1 and a synthetic resin coated with synthetic resin were added thereto. 42 g of RINKA 120UF (manufactured by Japanese Chemical Company, Phosphorus content 75%) was added and stirred until completely mixed to prepare a resin composition. The phosphorus content in the resin produced is 3%.

The resin composition prepared as described above is impregnated into glass fibers, followed by hot air drying to prepare a prepreg having a resin content of 43% by weight.

Eight pieces of this prepreg were laminated and placed on both sides with a copper foil having a thickness of 18 um, and then loaded. The press was heated and pressurized for 90 minutes at a temperature and pressure of 170 ° C. and 40 Kg / cm 2 to produce a 1.6 mm thick copper foil laminate. do.

The manufactured copper foil laminates were measured for solder blister by the time it takes to endure in a 288 ℃ lead bath, that is, the time it takes for the copper laminate to burst.The flame retardancy was measured by the vertical flame retardancy test method, UL94 test method. Measured by. The measurement results are shown in Table 1.

Example 2

Except for using the same amount of ferrocene in place of magnesium borate as a flame retardant catalyst of Example 1 after preparing a copper clad red plate under the same conditions as in Example 1, the lead heat resistance and flame resistance were measured. The measurement results are shown in Table 1.

Example 3

The lead heat resistance and flame retardance of the copper foil laminates were prepared under the same conditions as in Example 1 except that the phosphorus content in Example 1 was used without increasing the phosphorus content to 71 g without using magnesium hydroxide. The measurement results are shown in Table 1.

Example 4

A copper foil laminate was manufactured under the same conditions as in Example 1, except that 32.6 g of RINKA FR 140 (Japanese phosphorous product, phosphorus content 95%) was used instead of RINKA 120UF. After that, the lead heat resistance and flame retardancy were measured. The measurement results are shown in Table 1.

Example 5

After using magnesium borate, which is a flame retardant catalyst of Example 1, and using phosphorus content of 5%, the amount was increased to 71 g, and magnesium hydroxide was also used to increase the amount to 500 g. Heat resistance and flame resistance were measured. The measurement results are shown in Table 1.

Example 6

In Example 1, except that the same amount of aluminum hydroxide was used instead of magnesium hydroxide, a copper foil laminate was manufactured under the same conditions as in Example 1, and then lead heat resistance and flame resistance were measured. The measurement results are shown in Table 1.

Comparative Example 1

Except not using magnesium borate as a flame retardant catalyst in Example 1, after producing a copper foil laminate under the same conditions as in Example 1, the lead heat resistance and flame resistance were measured. The measurement results are shown in Table 1.

Comparative Example 2

The lead heat resistance and flame retardance of the copper foil laminates were prepared under the same conditions as in Example 1 except that the magnesium hydroxide and the coupling agent of Example 1 and Solution 1 were not used. The measurement results are shown in Table 1.

Comparative Example 3

Except that the flame retardant catalyst, red, magnesium hydroxide of solution 1 and the coupling agent in Example 1 were not used, and the epoxy resin was used in the same amount of the existing brominated flame retardant resin YDB424A80 (Epoxy equivalent 400, Kukdo Chemical). After producing a copper clad laminate under the same conditions as in 1, the heat resistance and flame resistance were measured. The measurement results are shown in Table 1.

Property measurement result Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 color Red Red Red Red Red Red Red Colorless Colorless Lead heat resistance (S / B, sec) 320 seconds 310 seconds 285 seconds 310 seconds 255 seconds 180 seconds 335 seconds 380 seconds 180 seconds Flame Retardant (UL94) V0 V0 V0 V0 V0 V0 V1 HB V0

Claims (9)

0.5 to 20 g of dicyanoamide curing agent and 0.01 to 3 g of amidazole-based curing accelerator, inorganic flame retardant, per 100 g of bromine-free bisphenol A epoxy, which may have a total phosphorus content of 2 to 20% in the epoxy resin. A resin composition for a flame-retardant epoxy copper foil laminate, characterized in that it contains 0 to 150 g, a flame retardant catalyst 1 to 10 g, and a coupling agent of 0.1 to 3% by weight based on the weight of the inorganic flame retardant aid. The resin composition according to claim 1, wherein the bisphenol A epoxy resin has an epoxy equivalent of 300 to 1,500. The resin composition according to claim 1, which has a structure of general formula (I). The resin composition of claim 1, wherein the curing accelerator is selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, and benzimidazole. The resin composition of claim 1, wherein the inorganic flame retardant auxiliary agent is at least one compound selected from the group consisting of magnesium hydroxide, aluminum hydroxide, antimony trioxide, and antimony pentoxide. The resin composition according to claim 1 or 5, wherein the inorganic flame retardant adjuvant is coated with a coupling agent. The resin composition according to claim 1, wherein the flame retardant catalyst is at least one compound selected from the group consisting of nickel compound, ferrocene and magnesium boride. The compound according to claim 7, wherein the nickel compound is selected from the group consisting of nickel (II) oxide, nickel (III) oxide, bis (8-hydroxyquinylino) nickel (II) and bis (acetylacetonate) nickel (II) A resin composition for flame retardant epoxy copper foil laminate. The resin composition according to claim 1, wherein the coupling agent is a titanate compound or a silane compound.