JPH10273520A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which has excellent flame retardancy and heat resistance in soldering with no halogen compounds, and hence is useful as a non-halogen material being further required in future. SOLUTION: This composition comprises (A) 100 pts.wt. phenol novolak epoxy resin or cresol novolak epoxy resin, (B) 5 to 50 pts.wt. maleimide compound having at least one maleimide moiety in one molecule thereof, (C) 5 to 50 pts.wt. curing agent of the formula, wherein each of R<1> and R<2> is an alkyl group or an aryl group and (D) 0.5 to 5 pts.wt. phosphorus component relative to 100 pts.wt. of the total amount of components A, B and C, as essential components, with the proviso that the amount of the nitrogen components is 2.0 to 10.0 pts.wt. relative to 100 pts.wt. of the total amount of the composition. It is preferred that the total amount of components A, B, C and D is 80% or more of the amount of the total solids of the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition having excellent flame retardancy without using a halogen-based flame retardant and usable for a long period of time, a prepreg and a prepreg using the same. It relates to a laminate.

[0002]

2. Description of the Related Art Thermosetting resins typified by epoxy resins are widely used for electric and electronic equipment parts due to their excellent properties, and are provided with flame retardancy to ensure fire safety. There are many cases. Conventionally, these resins have generally used a halogen-containing compound such as a brominated epoxy resin. Although these halogen-containing compounds have high flame retardancy, aromatic bromine compounds not only separate corrosive bromine and hydrogen bromide by pyrolysis,
Decomposition in the presence of oxygen can form highly toxic polybromodibenzofuran and polydibromobenzooxin. Further, it is extremely difficult to treat aging waste materials and refuse containing bromine. For these reasons, phosphorus compounds and nitrogen compounds have been widely studied as flame retardants instead of bromine-containing flame retardants, and the phosphorus component for obtaining flame retardancy is reduced by the synergistic effect of coexisting the phosphorus component and the nitrogen component. It is a well-known fact that we can do that. As the nitrogen component used at that time, aromatic amines are generally used.Aromatic amines are highly reactive with phenol novolak epoxy resins and cresol novolak epoxy resins, and the properties of the resin composition and prepreg are at room temperature. The drawback is that it is not maintained for a long time. For this reason, in order to obtain a laminate made of this resin composition, there has been a disadvantage that the usable period of the resin composition and the prepreg is limited to a very short period.

[0003]

In the present invention, in order to solve such a problem, by using the above-mentioned curing agent, the properties of the resin composition and the prepreg do not change over a long period of time. An object of the present invention is to express flame retardancy without using halogen due to the interaction between nitrogen and phosphorus by using a phosphorus compound in combination. That is,
An object of the present invention is to provide a resin composition, a prepreg, and a laminate obtained from the prepreg, which have high flame retardancy without adding a halogen compound and maintain the same characteristics for a long period of time.

[0004]

According to the present invention, there are provided (A) 100 parts by weight of a phenol novolak epoxy resin or a cresol novolak epoxy resin, and (B) a maleimide compound having at least one maleimide group in one molecule.
To 50 parts by weight, (C) 5 to 50 parts by weight of a curing agent represented by the following general formula (1), and

Embedded image (R ¹ and R ^{2 each} represent an alkyl group or an aryl group.) (D) The phosphorus component is required to be 0.5 to 5 parts by weight based on 100 parts by weight of the total of the components (A), (B) and (C). The composition contains as a component, and the nitrogen component is the total composition 100
2.0 to 10.0 parts by weight with respect to parts by weight.

[0005]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS As described above, a non-halogen flame retardant can be realized by the synergistic effect of coexistence of a phosphorus component and a nitrogen component. The mechanism is that the nitrogen compound promotes the decomposition and thermal condensation of the phosphorus component to generate polyphosphoric acid, and the polyphosphoric acid forms a film on the surface of the epoxy resin, resulting in a heat insulating effect and an oxygen blocking effect. It is thought to prevent burning. Further, in the present invention, a novolak epoxy resin or a maleimide compound having excellent heat resistance is used to obtain higher flame retardancy. Aromatic amines used as nitrogen components for flame retardancy have high reactivity with epoxy resins. Therefore, it is considered that if the reactivity of the aromatic amine is reduced, it is possible to reduce the change in the properties of the resin composition or the prepreg at room temperature. There are several methods for reducing the reactivity of the aromatic amine with the epoxy group. However, the amino group of the aromatic amine is substituted with an aryl group or alkyl group having a large steric hindrance.
It has been found that by using a tertiary amine, the reactivity with an epoxy group can be reduced. As described above, in the present invention, by using a secondary amine instead of a primary amine, the characteristics of the resin composition and the prepreg do not change over a long period of time. The main point of the technology is to express nonflammable flame by non-halogen by interaction.

As the component (A) used in the present invention, phenol novolak epoxy or cresol novolak epoxy can be cited, and phenol novolak epoxy is preferable in view of the fact that the methyl group is easily burned.

The maleimide compound having at least one maleimide group in one molecule of the component (B) used in the present invention includes N-methylmaleimide, N-phenylmaleimide,
N- (o-tolyl) maleimide, N- (o- or p-hydroxyphenyl) maleimide, N- (o- or m-methoxyphenyl) maleimide, N- (m-nitrophenyl) maleimide, N, N'- m-phenylenebismaleimide, N, N'-p-phenylenebismaleimide, N,
N'-4,4'-diphenylmethane bismaleimide,
Examples thereof include N, N'-4,4'-diphenylether bismaleimide and N, N'-4,4'-diphenylsulfonebismaleimide, but are not particularly limited thereto. N, N'- due to heat resistance, price, versatility, etc.
4,4'-Diphenylmethane bismaleimide is preferred.

The curing agent used in the present invention is represented by the above chemical formula (1), and includes p- (p-toluenesulfonylamide) diphenylamine, N, N'-di-2
-Naphthyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N-phenyl-N '
-Isopropyl-p-phenylenediamine, N-phenyl-N '-(1,3-dimethylbutyl) -p-phenylenediamine, N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl) -p- Examples include phenylenediamine, but N, N '
-Diphenyl-p-phenylenediamine is preferred.

The phosphorus component used in the present invention includes trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate and crexylenyl phosphate. Phosphoric acid esters such as zirdiphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tris (2,6-dimethylphenyl) phosphate and resorcinol diphenyl phosphate, and condensed phosphoric acid esters such as dialkylhydroxymethyl phosphonate are exemplified. However, the present invention is not particularly limited to these.

If the amount of component (B) is less than 5 parts by weight per 100 parts by weight of component (A), the effect on flame retardancy is small, and if it exceeds 50 parts by weight, heat resistance is undesirably reduced. If the amount of the component (C) is less than 5 parts by weight based on 100 parts by weight of the component (A), the curing of the resin becomes insufficient. If the amount exceeds 50 parts by weight, unreacted amino groups remain in the cured product, It is not preferable because it lowers the moisture resistance. The phosphorus component is a total of 1 of components (A), (B) and (C).
If the amount is less than 0.5 part by weight with respect to 00 parts by weight, the effect on flame retardancy is small, and if it exceeds 5 parts by weight, the solder heat resistance and the peel strength are undesirably reduced. If the nitrogen component is less than 0.5 part by weight based on 100 parts by weight of the total of components (A), (B) and (C), the effect on flame retardancy is small, and if it exceeds 10.0 parts by weight, water is easily absorbed. Is not preferred.

According to the present invention, the components (A), (B),
A resin composition containing the flame-retardant resin composition (C) and (D) in an amount of 80% by weight or more based on the total solid content is preferable. That is, the total amount of the components (A), (B), (C) and (D) is 1
An epoxy resin such as a bisphenol F type epoxy resin or a curing agent such as dicyandiamide is added to 00 parts by weight.
Up to 5 parts by weight may be added.

Although the flame-retardant resin composition of the present invention is used in various forms, a solvent is usually used when impregnating a substrate. The solvent used must have good solubility in a part of the composition, but a poor solvent may be used as long as it does not adversely affect the composition. The varnish obtained by dissolving the resin composition of the present invention in a solvent is impregnated into a substrate such as a glass woven fabric, a glass nonwoven paper, or a cloth having a component other than glass, and dried at 80 to 200 ° C. A prepreg can be obtained, and the prepreg is used for producing a laminated board for printed wiring boards by heating and pressing.
The resin composition of the present invention is a thermosetting resin composition having a high degree of flame retardancy without adding a halogen compound and maintaining the properties of a product for a long period of time, and is suitable for a laminated board and the like. It is used for

[0013]

【Example】

(Example 1) 100 parts by weight of a phenol novolak epoxy resin (Epiclon N-770 manufactured by Dainippon Ink and Chemicals) and 9 parts by weight of N, N'-4,4'-diphenylmethane bismaleimide (BMI-H manufactured by KI Kasei Co., Ltd.) Part, N,
N, N'-dimethylformamide was added to 11 parts by weight of N'-diphenyl-p-phenylenediamine, 5.5 parts by weight of dicyandiamide, and 45 parts by weight of triphenyl phosphate, and a varnish was added so that the nonvolatile content concentration became 60%. It was adjusted. At this time, the phosphorus component was 2.4% with respect to a total of 100 parts by weight of the epoxy resin, the maleimide compound, and the curing agent. Using this varnish, a glass cloth (thickness: 0.
100 parts of 18 mm (manufactured by Nitto Boseki Co., Ltd.) was impregnated with 80 parts of a varnish solid and dried in a drying oven at 150 ° C. for 5 minutes to prepare a prepreg having a resin content of 44.4%.

[0014] Six prepregs are stacked, and an electrolytic copper foil having a thickness of 35 µm is stacked on the upper and lower sides under a pressure of 40 kgf / cm.
^2. Heat-press molding was performed at a temperature of 190 ° C. for 120 minutes to obtain a double-sided copper-clad laminate having a thickness of 1.2 mm. The obtained laminate was measured for flame retardancy, solder heat resistance and peel strength. Table 1 shows the formulation and results. After leaving the prepreg in an environment of 23 ° C. for 30 days, six prepregs were stacked, and 35 μm thick electrolytic copper foil was stacked on top and bottom, and heated at a pressure of 40 kgf / cm ² and a temperature of 190 ° C. for 120 minutes. Pressure molding was performed to obtain a double-sided copper-clad laminate having a thickness of 1.2 mm. When this laminate was evaluated in the same manner as above, no change was observed in the characteristics.

(Examples 2 and 3 and Comparative Examples 1 to 6)
And the formulation shown in Table 2 except that
A double-sided copper-clad laminate was prepared in the same manner as described above. The results are shown in the lower columns of Tables 1 and 2. The flame retardancy of the obtained laminate is
The evaluation was made by the vertical method according to the UL-94 standard. Solder heat resistance and peel strength were measured in accordance with JIS C 6481. Solder heat resistance was determined by the appearance of abnormalities after immersion in a solder bath at 260 ° C. for 120 seconds after moisture absorption for 2 hours after boiling. Was examined.

[0016]

[Table 1]

[0017]

[Table 2] (1) Epicron N-770 manufactured by Dainippon Ink and Chemicals, Inc. (2) BMI-H manufactured by KI Kasei Co., Ltd. (3) Copper obtained by subjecting a prepreg to an environment of 23 ° C. for 30 days and then performing heat and pressure molding. Characteristics of upholstered laminate.

All of the laminates having the compositions shown in the examples are excellent in flame resistance and solder heat resistance. In addition, since the properties of the laminated board obtained by heating and pressing after leaving the prepreg at 30 ° C. for 30 days under the condition of 23 ° C. are maintained,
It can be seen that the characteristics are stable over a long period of time.

[0019]

Industrial Applicability The flame-retardant resin composition of the present invention has a high level of flame retardancy and solder heat resistance without adding a halogen compound, and maintains its properties for a long period of time. It is intended to provide a thermosetting resin composition useful as a material.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 63/00 C08L 63/00 C

Claims (4)

[Claims] (A) 100 parts by weight of a phenol novolak epoxy resin or a cresol novolak epoxy resin; (B) 5 to 50 parts by weight of a maleimide compound having at least one maleimide group in one molecule; 5 to 50 parts by weight of a curing agent represented by (1), and (R ¹ and R ² represent an alkyl group or an aryl group.) (D) The phosphorus component is required to be 0.5 to 5 parts by weight based on 100 parts by weight of the total of the components (A), (B) and (C). The composition is a resin composition containing as a component, and the nitrogen component is a total composition 1
The flame retardant resin composition is 2.0 to 10.0 parts by weight based on 00 parts by weight. 2. The component (A) or (D) according to claim 1.
A flame-retardant resin composition, wherein the total of the components is 80% or more of the entire solid content. 3. A prepreg obtained by impregnating a substrate with the flame-retardant resin composition according to claim 1 or 2. 4. A laminate obtained by laminating one or more prepregs according to claim 3.