KR100197945B1 - Antiflammable epoxy resin composition for laminating of copper sheet - 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.

The resin composition of the present invention is a resin composition comprising (A) 100 g of a bisphenol A-type epoxy resin having no bromine, (B) an amount of the epoxy resin having a total phosphorus content of 2 to 20% (E) inorganic flame-retardant auxiliary, 0 to 150 g, (F) 1 to 10 g of a flame retardant catalyst, (G) 0.1 to 3% by weight of an inorganic flame- Lt; / RTI >

The equivalent weight of the epoxy resin is 300 to 1,500, and the structure of the general formula (I) is shown.

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 flame-retardant epoxy copper-clad laminate

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.

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 an oriental laminate, a phenolic phenolic laminate (P) system and TBBA are used in combination, while in the case of a flame retardant epoxy copper laminate, only TBBA, a halogen type flame retardant, is used. When the flame-retardant epoxy copper-clad laminate is produced by using such a halogen-based flame retardant, toxic carcinogens such as polyhalogenated aromatic dioxin or dibenzofurane are generated when the flame retardant is burned. In particular, in the case of a polybrominated flame retardant, toxic carcinogens such as decarbromo phenyldoxide 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.

The present invention provides an epoxy resin composition for a flame retardant epoxy copper-clad laminate in which the harmfulness of a halogen-based compound is eliminated by using an inorganic flame retardant without using the halogen-based 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 type epoxy resin, an inorganic flame retardant auxiliary, a flame retardant catalyst, a coupling agent, a curing agent and a curing accelerator.

The bisphenol A type epoxy resin not containing bromine has an epoxy equivalent of 300 to 1,500 and is a basic composition of the resin composition.

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

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 epoxy resin used is 2 to 20% of the phosphorus content in epoxy resin. The amount of epoxy resin is different depending on the kind of epoxy resin. Therefore, the amount of epoxy resin is calculated based on phosphorus content in the 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.

When the inorganic flame-retardant additive and the flame-retardant catalyst are used together, the amount of the inorganic flame-retardant aid and the flame-retardant catalyst are different from each other, Is preferably 2 to 10% based on the phosphorus content.

The inorganic flame-retardant auxiliary 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 a metal hydroxide such as magnesium hydroxide or aluminum hydroxide, exhibits an excellent flame retarding effect.

The amount used is 0 to 150 PHR compared to 100 g of epoxy resin. Here, PHR means the number of grams (g) of the inorganic flame-retardant auxiliary added per 100 g of the epoxy resin. PHR used in the future indicates the number of grams (g) of various compounds per 100 g of epoxy. The use amount of the inorganic flame retarding auxiliary agent is also related to the usage amount of the inorganic flame retarding adjuvant. Therefore, it is preferable to use a small amount of the inorganic flame retarding adjuvant when using a small amount of inorganic flame retarding adjuvant.

Also, since the flame retardant performance is greatly improved when the flame retardant catalyst is used, it is preferable to use the inorganic flame retardant aid in an amount of 20 to 70 PHR based on 100 g of the epoxy resin.

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.

The flame retardant catalyst is one of the characteristic conditions of the present invention, and is a characteristic feature that greatly improves the flame retardancy of the flame retardant system as a small amount. Therefore, by reducing the amount of the flame retardant and the flame-retardant aid, the physical properties such as heat resistance of the laminate itself due to excessive use of the flame retardant and the flame-retardant aid can be suppressed.

Examples of the flame retardant catalyst to be used include nickel compounds such as nickel (II) oxide, nickel (III) oxide, bis (8-hydroxyquinolino) nickel (II) and bis (acetylacetonate) nickel (II) ) And magnesium borate. In case of nickel compounds, ferrocene or magnesium borate is preferable because it is a heavy metal substance. The amount to be used is 1 to 10 PHR compared to 100 g of epoxy resin. However, the amount to be used can be increased or decreased according to the composition of the flame retardant system.

The coupling agent is a titanate-based (silane-based) compound and is used in an amount of 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, and when used excessively, not only remains as a monomer material but also increases the cost.

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

Dicyanodiamide is used as the hardening agent, and the dosage is preferably 0.5 to 20 PHR. When the amount of the curing agent is less than 0.5 PHR, the amount of the curing agent is small. Thus, since the curing agent is not fully cured, the physical properties are remarkably low. When 20 PHR or more is used, the uncured agent remains in the monomer state 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 using too much, and the cost is increased by hindering the reaction of the curing agent.

The resin composition of the present invention has a problem that toxic carcinogens such as polyhalogenated aromatic dioxin or dibenzofuran are generated when a flame retardant epoxy copper laminate is used with 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 it is possible to solve the dispersion problem which occurs when using the inorganic flame retardant and the flame-retardant adjuvant.

The present invention uses a non-halogen flame retardant in combination with an inorganic flame retardant auxiliary such as a metal hydroxide to obtain a synergistic effect of flame retardancy, and even when a small amount of flame retardant is used, excellent flame retardancy can be obtained without changing physical properties of the copper clad laminate. Has an excellent effect of increasing lead heat resistance.

The main feature of the present invention is that the use of a flame retardant catalyst significantly improves the flame-retardant synergistic effect to significantly reduce the amount of the inorganic and / or organic flame-retardant adjuvant, thereby reducing the deterioration of the properties of the laminate itself, 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 titanate coupling agent KR38S (manufactured by Ajinomoto Co., Ltd.) is added to a 500 ml flask, and 500 ml of acetone is added to dissolve the solution. 300 g of magnesium hydroxide is added thereto, followed by stirring to prepare Solution 1. Then, 25 g of anodiamide was added to 200 g of N, N'-dimethylformamide and completely dissolved. Then, 1.5 g of 2-methylimidazole and 150 g of methylcellosol were added and stirred to complete solution 2 to prepare solution 2.

The epoxy resin YDB011A80 (epoxy equivalent: 400, vinyl chloride resin, Kukdo Chemical Co., Ltd.) (1000 g) was added to Solution 2 and stirred until completely mixed. Then, 30 g of magnesium borate as a flame retardant catalyst, And 42 g of RINKA 120 UF (product of Nippon Printing Co., Ltd., phosphorus content 75%) were added and stirred until thoroughly mixed to prepare a resin composition. The phosphorus content in the produced resin is 3%.

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 288 ° C lead-time, that is, the time taken for the copper-clad laminate to be blown up. Flame resistance was measured by UL94 experimental vertical flame- Respectively. The measurement joints are shown in Table 1.

[Example 2]

A copper-clad laminate was produced under the same conditions as in Example 1 except that the same amount of ferrocene was used in place of the magnesium borate as the flame retardant catalyst of Example 1, and the lead heat resistance and flame retardancy were measured. The measurement results are shown in Table 1.

[Example 3]

The heat resistance and the flame retardancy of the lead were measured after the copper clad laminate was produced under the same conditions as in Example 1, except that the magnesium hydroxide of the solution 1 in Example 1 was not used and the phosphorus content was increased to 71 g in phosphorus content of 5%. The measurement results are shown in Table 1.

[Example 4]

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

[Example 5]

A copper clad laminate was produced under the same conditions as in Example 1 except that the phosphorus content of 5% phosphorus was increased to 71 g and the amount of magnesium hydroxide was increased to 500 g without using the magnesium borate as the flame retardant catalyst of Example 1, And flame retardancy were measured. The measurement results are shown in Table 1.

[Example 6]

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

[Comparative Example 1]

A copper alloy laminate was produced under the same conditions as in Example 1, except that magnesium borate as a flame retardant catalyst in Example 1 was not 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 for using the flame retardant resin YDB424A80 (epoxy equivalent: 400, Kukdo Chemical Co., Ltd.) as an epoxy resin without using the flame retardant catalyst of Example 1, the magnesium hydroxide of the solution 1 and the coupling agent, 1, the lead heat resistance and the flame retardancy were measured. The measurement results are shown in Table 1.

Claims (9)

0.5 to 20 g of a dicyanoamide curing agent and 0.01 to 3 g of an amidazole-based curing accelerator per 100 g of the bromine-free bisphenol A-type epoxy resin in such an amount that the total phosphorus content in the epoxy resin can be 2 to 20% To 150 g of the flame retardant catalyst, 1 to 10 g of the flame retardant catalyst, and 0.1 to 3% by weight of the coupling agent based on the weight of the inorganic flame retardant auxiliary. The resin composition for a flame retardant epoxy copper-clad laminate according to claim 1, wherein the bisphenol A type epoxy resin has an equivalent weight of 300 to 1,500. The resin composition for a flame-retardant epoxy copper-clad laminate according to claim 1, wherein the resin has the structure of the general formula (I). The resin composition for a flame retardant epoxy copper-clad laminate according to claim 1, wherein the curing accelerator is selected from 2-methylimizazole, 2-ethyl-4-methylimidazole and benzimidazole. The resin composition for a flame retardant epoxy copper clad laminate 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 a flame retardant epoxy copper-clad laminate according to claim 1 or 5, wherein the inorganic flame-retardant auxiliary is coated with a coupling agent. The resin composition for a flame retardant epoxy copper clad laminate according to claim 1, wherein the flame retardant catalyst is at least one compound selected from the group consisting of nickel compounds, ferrocene, and magnesium boride. The method of claim 7, wherein the nickel compound is selected from the group consisting of nickel (II) oxide, nickel (III) oxide, bis (8- hydroxyquinolino) nickel (II) and bis (acetylacetonate) nickel And the resin composition for a flame-retardant epoxy copper-clad laminate. The resin composition according to claim 1, wherein the coupling agent is a titanate compound or a silane compound.