JP3126962B2 - Flame retardant epoxy resin composition, prepreg and laminated product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a halogen-free flame-retardant epoxy resin composition, a prepreg impregnated with the composition, and a laminate product of a laminate, a copper-clad laminate and a printed wiring board.

[0002]

2. Description of the Related Art In recent years, as environmental concerns around the world and concerns about safety for the human body have increased, electric and electronic devices have become less hazardous in addition to the conventional flame retardancy. The demand for high security is increasing.
That is, it is demanded that electric / electronic devices not only hardly burn, but also generate less harmful gas and smoke. Conventionally, printed wiring boards made of glass-based epoxy resin on which electrical and electronic components are mounted
Brominated epoxy resins containing bromine as a flame retardant, especially tetrabromobisphenol A type epoxy resins, are commonly used.

[0003] Such brominated epoxy resins have good flame retardancy, but can generate harmful hydrogen halide (hydrogen bromide) gas upon combustion, and can also generate brominated dioxins and furans. Therefore, its use is being suppressed.

Therefore, for example, various epoxy resin compositions containing a nitrogen compound, a phosphorus compound, an organic compound and the like have been developed (British Patent No. 1,112,139, Japanese Patent Application Laid-Open No. 2-269730). Reference).

[0005] However, the compounds described above have problems such as adversely affecting the curing of the epoxy resin and lowering the moisture resistance and heat resistance of the cured composition.

[0006]

An object of the present invention is to exhibit good flame retardancy without halogen (halogen free).
Another object of the present invention is to provide a flame-retardant epoxy resin composition which has solved the above-mentioned disadvantages of the prior art.

Further, the present invention provides a prepreg impregnated with such a flame-retardant epoxy resin composition, and a laminate, a copper-clad laminate and a printed wiring board manufactured using these prepregs. Also aim.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above-mentioned object, and as a result, a novel composition in which a cyclophosphazene compound and an epoxide compound are appropriately combined with a resin composition. The present invention has been found to exhibit good flame retardancy without containing halogen, to improve moisture resistance and heat resistance, and to achieve the above object, thereby completing the present invention.

That is, the present invention comprises (A) at least one cyclophosphazene compound, (B) at least one polyepoxide compound, (C) a curing agent for epoxy, and (D) an aluminum hydroxide filler as essential components,
(D) The composition ratio of the aluminum hydroxide filler in the composition
A flame-retardant epoxy for a halogen-free laminate, characterized in that the content of the halogen is 10% to 50% by weight and the content of the impurity halogen is 0.1% by weight or less for each of the compounds (A) to (C). It is a resin composition. Also,
A woven glass substrate prepreg impregnated with the flame-retardant epoxy resin composition, and a laminate, a copper-clad laminate, and a printed wiring board manufactured using the prepreg.

Hereinafter, the present invention will be described in detail.

The cyclophosphazene compound (A) used in the present invention is preferably a cyclophosphazene oligomer from the viewpoint of heat resistance, moisture resistance, flame retardancy and chemical resistance. The cyclophosphazene oligomer is represented by the following general formula, and its melting point is preferably 80 ° C. or higher.

[0012]

Embedded image (In the formula, X is a hydrogen atom or a substituent other than a halogen, and they may be the same or different from each other. In the formula, n represents an integer of 3 to 10.) Cyclophosphazene Examples of the substituent X other than halogen in the oligomer include organic groups such as an alkoxy group, a phenoxy group, an amino group, and an allyl group.

As the polyepoxide compound (B) used in the present invention, a glycidyl ether epoxy resin is preferred. This includes bisphenol A type epoxy resin,
Bisphenol F type epoxy resin, novolak type epoxy resin and the like can be mentioned, and these can be used alone or in combination of two or more. The epoxy resin also includes a glycidyl ether-based modified epoxy resin.
As the modified epoxy resin, for example, a BT resin or the like can be used.

As the epoxy curing agent (C) used in the present invention, dicyandiamide (DICY) and its derivatives,
Novolak-type phenolic resin, amino-modified novolak-type phenolic resin, polyvinylphenol resin, organic acid hydrazide, diaminomaleonitrile and its derivatives, melamine and its derivatives, amine imide, polyamine, amine, acid anhydride, polyamide, imidazole Can be used.

In the present invention, a curing accelerator is used, if necessary. As the curing accelerator, if necessary, a tertiary amine, imidazole, or aromatic amine used as a usual curing accelerator for epoxy resin is used. At least one of them can be used.

The bisphenol A epoxy resin or the like as the component (B) reacts bisphenol A with epichlorohydrin in the presence of an alkali, so that a reaction residue and impurity halogen as a reaction by-product remain.
(A) used in the present invention which is halogen-free
The component (C) and the curing accelerator are defined as those having an impurity halogen content of 0.1% by weight or less.

The filler (D) used in the present invention is an inorganic filler used as an auxiliary additive such as flame retardancy, and can be in a range that does not impair the resin properties such as resin impregnation. For this filler, aluminum hydroxide is used
You.

In the epoxy resin composition of the present invention, the compounding ratio of the compound and the like is such that (A) the phosphazene compound is 2%.
50 wt%, (D) aluminum hydroxide filler, 1
0 to 50% by weight. In addition, (A) component +
(D) Component is 20 to 70 weight% in a resin composition.
It is preferable to mix them.

The epoxy resin composition of the present invention is prepared by diluting the epoxy resin composition with a suitable organic solvent such as propylene glycol monomethyl ether to form a varnish, applying the varnish to a glass woven fabric substrate , impregnating it, and heating. A prepreg can be manufactured by the method. Also, a plurality of the prepregs may be laminated, and a copper foil may be laminated on one or both sides of the laminated structure, and then heated and pressed under a normal condition to obtain a glass epoxy copper clad laminate. At this time, a laminate can be obtained without using a copper foil. The multilayer board is
After forming a circuit on the copper-clad laminate (inner board) and then etching the copper foil, a prepreg and a copper foil are laminated on at least one side of the inner board, and this is, for example, 170
It can be manufactured by an ordinary method of heating and pressurizing at 100 ° C. and a pressure of 4 MPa for 100 minutes. Further, the printed wiring board can be manufactured by a usual method of forming a through hole in a copper-clad laminate or a multilayer board, performing through-hole plating, and then forming a predetermined circuit.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. "Part" in the following Examples and Comparative Examples
Means "parts by weight".

Example 1 Bisphenol A type epoxy resin epicoat 1001
651 parts (trade name of Yuka Shell Co., epoxy equivalent 456, resin solid content 70% by weight), YDCN-704P of cresol novolac epoxy resin (trade name of Toto Kasei Co., Ltd.
Epoxy equivalent 210, resin solid content 70% by weight) 300
Parts, 337 parts of bisphenol A type novolak resin (trade name, manufactured by Dainippon Ink and Chemicals, hydroxyl value 118, resin solid content 70% by weight), 301 parts of phenoxycyclophosphazene oligomer (melting point 100 ° C.), 30 parts of aluminum hydroxide
1 part and 2-ethyl-4-methylimidazole 0.9
Propylene glycol monomethyl ether (PGM) as a solvent was added to the mixture of parts to prepare an epoxy resin varnish having a resin solid content of 65% by weight.

Example 2 Bisphenol A type epoxy resin epicoat 1001
651 parts (trade name of Yuka Shell Co., epoxy equivalent 456, resin solid content 70% by weight), YDCN-704P of cresol novolak epoxy resin (trade name of Toto Kasei Co., Ltd.
Epoxy equivalent 210, resin solid content 70% by weight) 300
Propylene glycol monomethyl ether (PGM) as a solvent in a mixture consisting of 25 parts of dicyandiamide, 230 parts of phenoxycyclophosphazene oligomer (melting point 100 ° C.), 230 parts of aluminum hydroxide and 0.7 part of 2-ethyl-4-methylimidazole. Dimethylformamide was added to prepare an epoxy resin varnish having a resin solid content of 65% by weight.

Comparative Example 1 600 parts of a brominated epoxy resin Epicoat 5045 (trade name, manufactured by Yuka Shell Co., epoxy equivalent: 480, resin solid content: 80% by weight), bisphenol A type novolak resin (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) Propylene glycol monomethyl ether (PGM) as a solvent was added to a mixture consisting of 169 parts of a hydroxyl value of 118, a resin solid content of 70% by weight) and 2-ethyl-4-methylimidazole of 0.6 part to give a resin solid content of 65% by weight. An epoxy resin varnish was prepared.

Comparative Example 2 Epicoat 1001 of bisphenol A type epoxy resin
651 parts (trade name of Yuka Shell Co., epoxy equivalent 456, resin solid content 70% by weight), YDCN-704P of cresol novolac epoxy resin (trade name of Toto Kasei Co., Ltd.
Epoxy equivalent 210, resin solid content 70% by weight) 300
Parts, 337 parts of bisphenol A type novolak resin (trade name, manufactured by Dainippon Ink and Chemicals, hydroxyl value 118, resin solid content 70% by weight), triphenylene phosphate 541
Parts, 361 parts of aluminum hydroxide and 2-ethyl-4
Propylene glycol monomethyl ether (PG
M) was added to prepare an epoxy resin varnish having a resin solid content of 65% by weight.

Comparative Example 3 600 parts of brominated epoxy resin Epicoat 5045 (trade name, manufactured by Yuka Shell Co., epoxy equivalent: 480, resin solid content: 80% by weight), 13 parts of dicyandiamide, and 0.1 part of 2-ethyl-4-methylimidazole. Propylene glycol monomethyl ether (PGM) and dimethylformamide were added as solvents to the mixture of 5 parts to prepare an epoxy resin varnish having a resin solid content of 65% by weight.

Each of the epoxy resin varnishes obtained in Examples 1 and 2 and Comparative Examples 1 to 3 was continuously applied to a glass woven fabric.
It was impregnated and dried at a temperature of 160 ° C. to produce a prepreg. Eight prepregs using the 180 μm glass woven fabric thus obtained are superimposed, and a copper foil having a thickness of 18 μm is superimposed on both sides of the laminated body.
Heat and pressurize at a pressure of pa for 100 minutes, thickness 1.6mm
Was obtained. Table 1 shows the property evaluation results of the obtained copper-clad laminate.

Further, the same prepreg is superimposed, and a copper foil having a thickness of 35 μm is superimposed on both surfaces thereof.
Pressing produced an inner layer plate having a thickness of 0.8 mm. After forming a circuit on this inner layer plate and oxidizing the surface of the copper foil, the prepreg is superimposed on both surfaces thereof, and a copper foil having a thickness of 18 μm is superimposed on each of the prepregs. A 1.6 mm multilayer board was produced. Table 2 shows the results of evaluating the characteristics of the obtained multilayer board.

[0028]

[Table 1] * 1: 50 mm with copper foil on the surface removed by etching
After processing a sample of × 50 mm under the processing conditions in the table, 2
It was immersed in a solder bath at 60 ° C. for 30 seconds, and the presence or absence of blisters was observed.

[0029]

[Table 2] * 1: 50 mm with copper foil on the surface removed by etching
After processing a sample of × 50 mm under the processing conditions in the table, 2
It was immersed in a solder bath at 60 ° C. for 30 seconds, and the presence or absence of blisters was observed.

[0030]

As apparent from the above description and Tables 1 and 2, according to the present invention, excellent flame retardancy is obtained without containing halogen, and heat resistance, moisture resistance, chemical resistance and the like are improved. An epoxy resin composition is provided that provides an excellent glass epoxy laminate product. By using such a glass epoxy copper clad laminate, it is possible to provide a printed wiring board having good environmental characteristics and excellent in various characteristics.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08K 3:22 5: 5399) (72) Inventor Hiroki Kamiya 9-2 Chidoricho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Toshiba Chemical Corporation Kawasaki In the factory (56) References JP-A-10-259292 (JP, A) JP-A-8-225714 (JP, A) JP-A-61-113613 (JP, A) JP-A-3-221518 (JP, A) JP-A-11-181429 (JP, A) JP-A-63-349 (JP, A) JP-A-61-120850 (JP, A) JP-A-11-124489 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08L 63/00-63/10 B32B 27/38 C08J 5/24 C08K 5/5399 C08K 3/22

Claims (8)

(57) [Claims] 1. An essential component comprising (A) at least one cyclophosphazene compound, (B) at least one polyepoxide compound, (C) a curing agent for epoxy, and (D) an aluminum hydroxide filler,
(D) The composition ratio of the aluminum hydroxide filler in the composition
A flame-retardant epoxy for a halogen-free laminate, characterized in that the content of the halogen is 10% to 50% by weight and the content of the impurity halogen is 0.1% by weight or less for each of the compounds (A) to (C). Resin composition. 2. A method according to claim 1, wherein the cyclophosphazene compound (A) is a cyclophosphazene oligomer represented by the following general formula: (Where X is a hydrogen atom or a substituent other than halogen, and they may be the same or different from each other. In the formula, n represents an integer of 3 to 10). The flame-retardant epoxy resin composition for a halogen-free laminate according to claim 1 . 3. The flame-retardant epoxy resin composition for a halogen-free laminate according to claim 2 , wherein (B) the polyepoxide compound is a glycidyl ether epoxy resin. 4. The curing agent for epoxy (C) is dicyandiamide and its derivative, novolak-type phenol resin, amino-modified novolak-type phenol resin, polyvinylphenol resin, organic acid hydrazide, diaminomaleonitrile and its derivative, and melamine and its derivative. The flame-retardant epoxy resin composition for a halogen-free laminate according to claim 3 , which is at least one curing agent selected from the group consisting of amine imide, polyamine, amine, acid anhydride, polyamide and imidazole. 5. A prepreg comprising a glass woven fabric impregnated with the epoxy resin composition according to any one of claims 1 to 4 . 6. A laminate comprising the prepreg according to claim 5, wherein the epoxy resin composition is cured. 7. A copper-clad laminate comprising a substrate made of the prepreg according to claim 5, wherein the epoxy resin composition is cured, and a copper foil bonded to at least one surface of the substrate. 8. A printed wiring board comprising: a substrate made of the prepreg according to claim 5, wherein the epoxy resin composition is cured; and a copper foil circuit formed on at least one surface of the substrate.