JP2002206018A - Flame-retardant epoxy resin and lamination-associated product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phosphorus-containing epoxy resin exhibiting excellent flame retardancy without containing a halogen, having excellent mechanical characteristics and pot life, and capable of providing a glass-epoxy laminated product such as a printed circuit board, and further to provide a lamination- associated product. SOLUTION: This phosphorus-containing epoxy resin is obtained by reacting a phosphorus compound represented by the general formula, with an epoxy resin, and the flame-retardant epoxy resin composition for a halogen-free laminated board contains the phosphorus-containing epoxy resin and a curing agent for the epoxy resin as essential components. The glass base prepreg is impregnated with the flame-retardant epoxy resin composition, and the laminate, the copper-clad laminate and the printed circuit board are produced by using the prepreg.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphorus-containing epoxy resin and an epoxy resin composition containing the same, a prepreg, a laminate, a copper-clad laminate, and a laminate-related product of a printed wiring board, which have particularly excellent properties. It is a halogen-free flame-retardant product.

[0002]

2. Description of the Related Art In recent years, with the growing concern about global environmental problems and safety to human bodies, electric and electronic devices have been required to be less harmful in addition to the conventional requirement of flame retardancy. There is an increasing demand for higher security. That is, it is demanded that electric and electronic devices not only hardly burn, but also generate less harmful gas and dust. Conventionally, printed wiring boards on which electric and electronic components are mounted are usually made of a substrate made of glass epoxy, but the epoxy resin used there is a brominated epoxy resin containing bromine that acts as a flame retardant, especially Tetrabromobisphenol A type epoxy resin is generally 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). No., JP-A-11-
279258).

[0005] However, these compounds have problems such as adversely affecting the curing of the epoxy resin, lowering the mechanical properties, and shortening the pot life of the resin.

[0006]

An object of the present invention is to exhibit good flame retardancy without halogen (halogen free).
In addition, an object of the present invention is to provide an epoxy resin which has solved the above-mentioned disadvantages of the prior art and a flame-retardant epoxy resin composition containing the same. Further, another invention relates to a prepreg impregnated with such a flame-retardant epoxy resin composition,
Another object is to provide a laminate, a copper-clad laminate, and a printed wiring board manufactured using these prepregs.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have reacted a specific phosphorus compound represented by the following general formula 3 with an epoxy resin. With the new phosphorus-containing epoxy resin obtained,
The present invention has been found to exhibit good flame retardancy without containing halogen, to improve mechanical properties and the like, and to achieve the above object, and to complete the present invention.

That is, the phosphorus-containing epoxy resin of the present invention comprises:
A phosphorus-containing epoxy resin obtained by reacting a phosphorus compound represented by the following general formula or a derivative thereof with an epoxy resin, and an epoxy resin composition containing the phosphorus-containing epoxy resin and a prepreg such as a prepreg. Product.

[0009]

Embedded image (Wherein, R represents a hydrogen atom, a phenoxy group or an alkyl group) Hereinafter, the present invention will be described in detail.

The epoxy resin used for synthesizing the phosphorus-containing epoxy resin of the present invention can be used without any particular limitation as long as it is an epoxy resin containing no halogen. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin and the like can be used alone or in combination of two or more. The epoxy resin also includes a modified epoxy resin. As the modified resin, for example, a BT resin or the like can be used. Since the higher the phosphorus content of the synthesized phosphorus-containing epoxy resin, the better the flame resistance, the epoxy resin used preferably has a smaller molecular weight.
The reaction between the phosphorus compound and the epoxy resin may be a known method, and an organic solvent or a catalyst can be used if necessary. Further, the phosphorus content is preferably 2 to 5%. This content is 2
If it is less than 5%, good flame retardancy cannot be obtained, and if it exceeds 5%, the resin viscosity becomes high, impregnating property to the base material becomes poor, and various properties after curing may be deteriorated.

The curing agent for epoxy used in the epoxy resin composition of the present invention is dicyandiamide (DIC).
Y) 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 salt, molecular sieve, amine, acid anhydride At least one of a substance, a polyamide and an imidazole
Seeds can be used.

If necessary, tertiary amines, imidazoles, aromatic amines and the like which are used as ordinary epoxy resin curing accelerators can be used.

Among the above curing agents, amino-modified novolak type phenol resins are preferred for improving alkali resistance. In particular, a novolak type phenol resin having a triazine structure is preferable, and examples thereof include brands such as LA-7051, 7052, and 7054 manufactured by Dainippon Ink and Chemicals, Inc.

In the epoxy resin composition of the present invention, inorganic fillers such as talc, silica, alumina, aluminum hydroxide and magnesium hydroxide can be used as auxiliary additives for imparting flame retardancy. . These auxiliary additives can be used in a range that does not impair the resin properties such as resin impregnating property, and they can be used alone or in combination of two or more. The compounding ratio of the additive is preferably less than 30% by weight based on the resin composition. If it exceeds 30% by weight, the mechanical properties deteriorate, which is not preferable.

[0015] The prepreg of the present invention is prepared by diluting the epoxy resin composition of the present invention with a suitable organic solvent such as propylene glycol monomethyl ether to form a varnish. Applied to
It can be manufactured by a usual method of impregnating and heating. Further, a plurality of the prepregs are laminated, and a copper foil is laminated on one side or both sides of the laminated structure, and then heated and pressed under ordinary conditions 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 formed by forming a circuit on a copper-clad laminate (inner board), etching the surface of the copper foil, then laminating a prepreg and copper foil on at least one side of the inner board, and for example, 170 ° C., 4 MPa It can be manufactured by a usual method of heating and pressing at a pressure of 60 minutes. Further, the printed wiring board can be manufactured by a usual method such as forming a through hole in a copper-clad laminate or multilayer board, plating the through hole, and then forming a predetermined circuit.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, “parts” means “parts by weight”.

[Synthesis Example 1 of Phosphorus-Containing Epoxy Resin] Bisphenol F type epoxy resin (epoxy equivalent: 169) 7
0 parts and PPQ (trade name, manufactured by Hokko Chemical Industry Co., Ltd.) [2-
(Diphenylphosphinyl) hydroquinone], 30 parts of triphenylphosphine was added as a reaction catalyst, and the mixture was reacted at 150 ° C. for 4 hours to obtain a phosphorus content of 3.0.
5% epoxy resin was synthesized. Thereafter, the synthesized resin was cooled to 100 ° C., and propylene glycol monomethyl ether was added and mixed to prepare a phosphorus-modified epoxy resin having a nonvolatile content of 70%.

[Synthesis Example 2 of Phosphorus-Containing Epoxy Resin] Bisphenol F type epoxy resin (epoxy equivalent: 169) 7
9 parts and PPQ (trade name, manufactured by Hokko Chemical Industry Co., Ltd.) [2-
(Diphenylphosphinyl) hydroquinone], 21 parts of triphenylphosphine as a reaction catalyst was added and reacted at 150 ° C. for 4 hours to obtain a phosphorus content of 2.1.
0% epoxy resin was synthesized. Thereafter, the synthesized resin was cooled to 100 ° C., and propylene glycol monomethyl ether was added and mixed to prepare a phosphorus-modified epoxy resin having a nonvolatile content of 70%.

Example 1 58 parts of the phosphorus-containing epoxy resin synthesized in Synthesis Example 1 above,
Phenolite L, a nitrogen-modified novolak phenolic resin
A-7051 (trade name, manufactured by Dainippon Ink and Chemicals, Inc., hydroxyl value: 128, resin solid content: 70% by weight) was mixed with 17 parts of aluminum hydroxide and 25 parts of aluminum hydroxide, and propylene glycol monomethyl ether (PGM) was added as a solvent to the resin. An epoxy resin composition having a solid content of 65% by weight was prepared.

Example 2 80 parts of the phosphorus-containing epoxy resin synthesized in Synthesis Example 1 above,
Phenolite L, a nitrogen-modified novolak phenolic resin
A-7051 (trade name, manufactured by Dainippon Ink and Chemicals, Inc., hydroxyl value: 128, resin solid content: 70% by weight) To a mixture of 20 parts, propylene glycol monomethyl ether (PGM) was added as a solvent to give a resin solid content of 65% by weight. An epoxy resin composition was prepared.

Example 3 61 parts of a phosphorus-containing epoxy resin epicron N-865-70M synthesized in Synthesis Example 1 above, a bisphenol A type novolak resin (trade name, manufactured by Dainippon Ink and Chemicals, hydroxyl value 118, resin solid content 70 weight) %) And propylene glycol monomethyl ether (PGM) as a solvent was added to a mixture composed of 14 parts and 25 parts of aluminum hydroxide to prepare an epoxy resin composition having a resin solid content of 65% by weight.

Example 4 73 parts of the phosphorus-containing epoxy resin synthesized in Synthesis Example 2 above,
To a mixture of 2 parts of dicyandiamide solution (solvent dimethylformamide, solid content 10% by weight) and 25 parts of aluminum hydroxide, propylene glycol monomethyl ether (PGM) was added as a solvent to prepare an epoxy resin composition having a resin solid content of 65% by weight. did.

Comparative Example 1 Epicron 1051 of bisphenol A type epoxy resin
27 parts of -75M (trade name, manufactured by Dainippon Ink & Chemicals, Inc., epoxy equivalent: 473, resin solid content: 75% by weight), phenol novolak type epoxy resin EPICLON N-770-7
0M (trade name, manufactured by Dainippon Ink and Chemicals, epoxy equivalent 19
0, resin solid content 70% by weight) 20 parts, nitrogen-modified novolak type phenol resin LA-7051 (trade name, manufactured by Dainippon Ink & Chemicals, Inc., hydroxyl value 128, resin solid content 70% by weight) 21 parts, condensed phosphoric acid Ethylene PX-200 (trade name, manufactured by Daihachi Chemical Co., Ltd., phosphorus content 9%), propylene glycol monomethyl ether (PGM) was added as a solvent to a mixture of 20 parts of aluminum hydroxide, and an epoxy having a resin solid content of 65% by weight was added. A resin composition was prepared.

Comparative Example 2 75 parts of a brominated epoxy resin, Epicron 1121-75M (trade name, manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent: 490, resin solid content: 75% by weight), phenol novolak type epoxy resin Epicron N-770-70M (Dai Nippon Ink and Chemicals, epoxy equivalent 190, resin solid content 7
Propylene glycol monomethyl ether (PGM) as a solvent was added to a mixture consisting of 9 parts of 0 parts by weight (0% by weight) and 16 parts of a dicyandiamide solution (solvent dimethylformamide, solids of 10% by weight) to obtain an epoxy resin composition having a resin solids of 65% by weight. Prepared.

The epoxy resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were added with 2-methyl-4- as a curing accelerator.
The gel time was set to 210 seconds by adding ethyl imidazole, each was continuously applied and impregnated on a glass glass woven fabric, and dried at a temperature of 160 ° C. to produce a prepreg.
Eight prepregs using the 180-μm glass woven fabric obtained in this manner are superposed, and a thickness of 18
The copper foil of μm was overlapped and heated and pressed at a temperature of 170 ° C. and a pressure of 4 Mpa for 100 minutes to obtain a glass epoxy copper clad laminate having a thickness of 1.6 mm. Table 1 shows the property evaluation results of the obtained copper-clad laminate and the used prepreg.

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. The prepreg was superimposed on both sides of the inner layer plate, and a copper foil having a thickness of 18 μm was superimposed thereon, and heated and pressed similarly to produce a 1.6 mm thick multilayer plate. Table 2 shows the results of evaluating the characteristics of the obtained multilayer board.

[0027]

[Table 1] * 1: Measured according to JIS-C-6481, * 2: Measured according to UL94 flame retardancy test, * 3: Sample was placed in a 260 ° C. solder bath for 8 minutes according to JIS-C-6481. Floating, the presence of blisters was observed. ◎: None of all samples, ○: Some of the samples, △: Most of the samples, X: All of the samples, * 4: One glass cloth on the surface was peeled off. JIS-C-
Measured according to 6481. * 5: Measured according to JIS-C-6481. * 6: The prepreg was treated at 40 ° C. for 10 days, and the gel time was measured. The numerical values indicate the percentage of the gel time after treatment when the initial value is 100%.

[0028]

[Table 2] * 1: Measured according to JIS-C-6481. * 2: A sample cut to 50 mm × 50 mm was boiled for 4 hours, floated in a solder bath at 260 ° C. for 30 seconds, and observed for blisters. ◎: none in all samples, ○: some samples, △: most samples, ×: all samples

[0029]

As apparent from the above description and Tables 1 and 2, the epoxy resin of the present invention exhibits excellent flame retardancy without containing halogen, and has excellent mechanical properties and pot life. An epoxy resin composition is provided that provides a glass epoxy laminate product. If such a glass epoxy copper clad laminate is used, it gives good environmental properties,
And a printed wiring board excellent in various characteristics can be manufactured.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tsuyoshi Sugiyama 9-2 Chidoricho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Inside the Kawasaki Plant of Toshiba Chemical Corporation (72) Inventor Hiroki Kamiya 9 Chidoricho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture No. 2 Toshiba Chemical Co., Ltd. Kawasaki Factory F-term (reference) 4F072 AB09 AD28 AD35 AG03 AG16 AH21 AK05 AL12 AL13 4F100 AA19H AB17B AB33B AG00A AK33 AK53A AL06A BA02 CA02 DG01A DH01A GB43 JJ07 4J036 FB07 DC08 JA11

Claims (6)

[Claims] 1. A phosphorus-containing epoxy resin obtained by reacting a phosphorus compound represented by the following general formula or a derivative thereof with an epoxy resin. Embedded image (Wherein, R represents a hydrogen atom, a phenoxy group or an alkyl group) 2. An epoxy resin composition comprising the phosphorus-containing epoxy resin according to claim 1 and a curing agent for epoxy as essential components. 3. A prepreg, wherein a glass substrate is impregnated with the epoxy resin composition according to claim 2. 4. A laminate comprising the prepreg according to claim 3, wherein said epoxy resin composition is cured. 5. A copper-clad laminate comprising a substrate made of the prepreg according to claim 3, wherein the epoxy resin composition is cured, and a copper foil bonded to at least one surface of the substrate. 6. A printed wiring board, comprising: a substrate made of the prepreg according to claim 3, wherein the epoxy resin composition is cured; and a copper foil circuit formed on at least one surface of the substrate.