JPH05320333A - Flame-retardant curable resin composition - Google Patents

Abstract

PURPOSE:To obtain the curable resin composition having excellent flame retardance, heat resistance, water resistance, mechanical strength, adhesiveness to metals and electrical characteristics by blending a maleimide compound with an alkenylphenol compound and a bromine-containing polycarbonate. CONSTITUTION:100 pts.wt. total amounts of (A) 20-80 pts.wt. maleimide compound of formula I (D is C-C double bond-containing bifunctional group) [preferably N,N'-(methylenedi-p-phenylene)dimaleimide] and 80-20 pts.wt. alkenylphenol compound of formula II (n is 0-5; t and U are 0 or 1; R<1> to R<3> are H or methyl; X<1> and X<2> are CH2, SO2, etc.) (preferably 3,3'-dimethallyl-bisphenol A) are further mixed with (C) a bromine-containing polycarbonate to give the objective composition. When tetrabromobisphenol A is used as a bifunctional bromine- containing phenol, preferably the objective composition having excellent strength and electrical characteristics is obtained.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is excellent in flame retardancy, heat resistance, water resistance, mechanical strength, has a low dielectric constant, and has good adhesion to copper foil. The present invention relates to a curable resin composition which is useful as a material, a heat-resistant molded product, a composite material, a heat-resistant filler, a heat-resistant coating agent, and the like, and is particularly excellent for copper-clad laminate applications.

[0002]

2. Description of the Related Art In recent years, heat resistance and high reliability of a resin forming a copper clad laminate have been demanded with the multilayered printed wiring board and the development of element mounting technology. Widely used. Examples thereof include resins obtained by copolymerizing bismaleimides and diamines such as diaminodiphenylmethane.

However, a laminated board using this resin is
Since the heat resistance of solder after absorbing water such as when it is immersed in a plating bath is poor and the dielectric constant is high, a material having a lower dielectric constant has been desired for applications such as computer substrates for performing high-speed calculation.

Laminates using a resin obtained by copolymerizing bismaleimides and ordinary alkenylphenols are
Although it has features such as high heat resistance, high solder heat resistance after absorbing water, and low dielectric constant, it is unsuitable for use as a printed wiring board due to insufficient flame retardancy.

In general, a method of adding a flame retardant such as a bromine compound has been adopted for the purpose of imparting flame retardancy to resins, and decabromodiphenyl ether or brominated epoxy resins have been used for bismaleimide resins. .. However, it has been pointed out that the former low-molecular weight compound having no reactivity with the resin may be scattered outside the resin during use, resulting in deterioration of the resin. In addition, there is a risk that the environment will be adversely affected by scattering outside the resin. On the other hand, the latter brominated epoxy resin does not have such a risk because it takes a cross-linked structure by using an appropriate curing agent, but since the decomposition temperature is low, the original heat resistance of the bismaleimide resin is fully utilized. I couldn't.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of conventional thermosetting resins, and improves flame retardancy, heat resistance, water resistance, mechanical strength and adhesiveness with metals. An object of the present invention is to provide a thermosetting resin having excellent electrical characteristics such as excellent low dielectric constant.

[0007]

Means for Solving the Problems The present inventors have completed the present invention as a result of extensive studies to solve the above problems. That is, in the present invention, 20 to 80 parts by weight of (A) and 80 to 20 parts by weight of (B) (however, (A) +
(B) = 100 parts by weight) and the above-mentioned (C).

Maleimide compound (A) used in the present invention
Is a compound having one or more groups represented by the general formula (i) in one molecule, and specific examples thereof include N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N. -Hexylmaleimide,
N-octyl maleimide, N-dodecyl maleimide, N
-Cyclohexylmaleimide, N-phenylmaleimide, Np-hydroxyphenylmaleimide, Np-
Carboxyphenyl maleimide, N-p-chlorophenyl maleimide, N-o-chlorophenyl maleimide, N
-2,5-diethylphenylmaleimide, N-2,5-
Dimethylphenylmaleimide, N-o-methylphenylmaleimide, N-o-tolylmaleimide, Nm-tolylmaleimide, Np-tolylmaleimide, N-α-naphthylmaleimide, N-benzylmaleimide, Np-
Xylylmaleimide, N-o-xylylmaleimide, N
-M-xylylmaleimide, N, N'-methylenedimaleimide, N, N'-ethylenedimaleimide, N, N'-
Hexamethylene dimaleimide, N, N'-dodecamethylene dimaleimide, N, N'-m-phenylene dimaleimide, N, N'-p-phenylene dimaleimide, N, N '
-(Oxydi-p-phenylene) dimaleimide, N,
N '-(methylenedi-p-phenylene) dimaleimide,
N, N '-(methylenedi- (3-methyl-p-phenylene)) dimaleimide, N, N'-(methylenedi- (3-
Ethyl-p-phenylene)) dimaleimide, N, N'-
(Methylenedi- (3-methyl-5-ethyl-p-phenylene)) dimaleimide, N, N '-(2,2-bis-
(4-phenoxyphenyl) propane-dimaleimide,
N, N'-2,4-tolylene dimaleimide, N, N'-
2,6-tolylene dimaleimide, N, N'-m-xylylene dimaleimide, N, N'-oxydipropylene dimaleimide, ethylenedioxy-bis-N-propyl maleimide and oxy-bis-N-ethyl maleimide. Is mentioned. If desired, two or more of these may be used in combination.

Among the above, N, N '-(methylenedi-
It is preferable to use p-phenylene) dimaleimide because the melt viscosity decreases and the workability improves when heated and mixed with other components constituting the present invention.

The alkenylphenol compound (B) is a compound represented by the above general formula (ii), and specific examples thereof are 4,4'-dihydroxy-3,3'-diallylbiphenyl and 3,3'-diallylbisphenol A. , 3, 3 '
-Diallyl bisphenol F, 4,4'-dihydroxy-3,3'-diallyl-diphenyl sulfone, 4,4 '
-Dihydroxy-3,3'-diallyl-diphenyl ether, 4,4'-hydroxy-3,3'-diallylbenzophenone, 2,2'-bis- (4-hydroxy-3-)
Allyl-phenyl) -hexafluoropropane, 4,
4'-dihydroxy-3,3'-dimethallyl-biphenyl, 3,3'-dimethallyl-bisphenol A, 3,
3'-dimethallyl-bisphenol F, 4,4'-dihydroxy-3,3'-dimethallyl-diphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethallyl-
Diphenyl ether, 4,4'-hydroxy-3,3 '
-Dimethallyl-benzophenone and 2,2'-bis-
Examples thereof include (4-hydroxy-3-methallyl-phenyl) -hexafluoropropane, and compounds having an allyl group or a methallyl group in the ortho position with respect to the phenolic hydroxyl group of phenol novolac and cresol novolac. If desired, two or more of these may be used in combination.

Among the above, n = in the general formula (ii)
It is preferable to use one having 0, u = 1 and X ² of an isopropylene group or a methylene group because both heat resistance and workability are improved. Examples of such a kind include 3,3′-diallylbisphenol A, 3,3′-diallylbisphenol F, 3,3′-dimethallyl-bisphenol A and 3,3′-dimethallyl-bisphenol F, and particularly 3,3′-dimethallyl-bisphenol A is
This is preferable because it has the effect of lowering the dielectric constant.

The bromine-containing polycarbonate (C) is a polymer obtained by polymerizing a divalent phenol having at least one bromine atom in one molecule with phosgene or ethylene carbonate by a known method. It is an oligomer. This bromine-containing polycarbonate (C)
Specific examples of the divalent bromine-containing phenols for obtaining are tetrabromobisphenol A, tetrabromobisphenol S, tetrabromobisphenol F, dihydroxytetrabromobiphenyl, dihydroxytetrabromodiphenyl ether, dihydroxytetrabromobenzophenone, dihydroxyoctabromodiphenyl ether. , Tetrabromophenolphthalein, tetrabromophenol blue and the like. If desired, two or more kinds of these compounds may be used. Further, naturally, a monobromide, a dibromide, a tribromide and the like, which are by-produced during the synthesis of these tetrabrominates, can also be used.

Of the above compounds, the use of tetrabromobisphenol A is preferable because it has excellent strength and electrical characteristics, and has a good balance of properties such as compatibility with the compounds (A) and (B).

Further, for the purpose of improving compatibility, electric characteristics, etc., divalent phenols containing no bromine atom are added to the above 1
It can also be used by copolymerizing with divalent phenols containing one or more bromine atoms in the molecule. Examples of these phenols include bisphenol A, bisphenol F, bisphenol S, bisphenol AD, 3,
3 ', 5,5'-tetramethylbisphenol A, 3,
There are 3 ', 5,5'-tetramethylbisphenol F, dihydroxybenzophenone, dihydroxydiphenyl ether, dihydroxybiphenyl, hydroquinone, catechol, resorcinol, dihydroxynaphthalene and bisphenol AF.

The average molecular weight of the above (C) is from 1000 to 20.
The range of 000 is preferable. If the average molecular weight is less than 1000, the heat resistance of the final resin cured product may be insufficient, and if it exceeds 20,000, the solubility in the resin will decrease and the viscosity of the resulting resin composition will be too high. This is not preferable because the workability is deteriorated.

The composition of the present invention contains the compound (A) in an amount of 20 to 20%.
80 parts by weight, more preferably 40 to 60 parts by weight, and 80 to 20 parts by weight of the compound (B), more preferably 60 to 60 parts by weight.
40 parts by weight (however, (A) + (B) = 100 parts by weight),
And (C). The amount of bromine in (C) is in the range of 1 to 20% by weight, with the total amount of the components (A), (B), (C) and other combustible additives in the resin composition being 100% by weight. It is preferable that the composition be blended as follows.

If the amount of the compound (A) is more than 80 parts by weight,
The obtained resin composition is fragile and tends to have insufficient strength, and when the amount of the compound (B) is more than 80 parts by weight, the obtained resin composition is likely to be colored or deformed, which are both unsuitable.

In the blending of (C), the bromine content is 1% based on the total amount of the components (A), (B), (C) and other combustible additives in the resin composition as 100% by weight. If it is less than 20% by weight, the flame retardancy of the resulting resin composition cannot be obtained, and if it exceeds 20% by weight, (C) is uniformly dissolved in the resin varnish in the production of the resin varnish. It becomes difficult to do so, and the heat resistance of the resin is lowered, which is not preferable.

If desired, a radical reaction initiator may be added to the resin composition of the present invention for the purpose of lowering the temperature during curing.

To the resin composition of the present invention, a coupling agent such as a silane coupling agent can be added, if necessary, for the purpose of improving the adhesive strength to a metal such as a copper foil, and a particularly preferred cup. The ring agent is a silane coupling agent having an epoxy group.

If desired, a reactive diluent such as allylphenol or eugenol may be added to the resin composition of the present invention for the purpose of decreasing the viscosity during compounding.

A flame retardant aid such as antimony trioxide may be added to the resin composition of the present invention, if necessary, for the purpose of further enhancing the flame retarding effect of the flame retardant (C). ..

The method of blending each component in obtaining the composition of the present invention is a method of dissolving the above (A), (B) and (C) in an organic solvent as they are; 100 to 100 of (A) and (B). Two
It is heated and melted at 00 ° C. to obtain a prepolymer, which is (C)
And (B) are both dissolved in an organic solvent; (A) and (B) are heated in an organic solvent to obtain a prepolymer solution, and (C) is mixed therein.

The resin composition thus obtained is preferably used as a resin varnish for laminated boards, but it includes talc, zinc white, silica, ceramic powder, inorganic fillers such as carbon fiber and glass fiber, and butadiene rubber. , NBR, and other organic additives can also be added.

On the other hand, in addition to the above-mentioned use as a solution type resin varnish, a hot melt mixture of (A) and (B) or a mixture of prepolymer and (C) is melted at 100 to 150 ° C. It is also possible to use it for impregnation while keeping it at.

The resin varnish or molten mixture obtained by the above-mentioned method is impregnated into a base material such as glass fiber cloth, aramid fiber cloth or cellulose paper, and the temperature is 100 to 200 ° C.
Can be heated for a suitable time at a temperature of 2 to form a semi-cured prepreg, which can be heated and pressed together with a copper foil to form a copper clad laminate.

[0027]

The resin composition obtained by the present invention is excellent in flame retardancy, heat resistance, water resistance, mechanical strength, adhesion to metal, and has excellent electrical characteristics such as low dielectric constant. The reason for this is not clear, but bromine in the bromine-containing polycarbonate as the component (C) is a negative catalyst for the combustion of the resin,
Also, it does not deteriorate even at the temperature during lamination molding and the temperature during soldering, and since the component (C) is a polymer that has good compatibility with the components (A) and (B), it scatters during use. It is presumed that this is because the physical properties are not deteriorated.

[0028]

Example 1 48 parts (parts by weight; the same applies hereinafter) of 3,3'-dimethallyl-bisphenol A, N, N '.
52- (methylenedi-p-phenylene) dimaleimide
Parts and 43 parts of N-methyl-2-pyrrolidone as a solvent were stirred at 150 ° C. for 1.5 hours to obtain a mixture, and 84 parts of methyl ethyl ketone and β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane ( Nippon Unicar Co., Ltd .: A-186) 5 parts, 2,5-dimethyl-2,
2.5 parts of 5-di (t-butylperoxy) -3-hexyne (manufactured by NOF CORPORATION: Perhexin 25B) and brominated polycarbonate (manufactured by Teijin Chemicals: Fireguard 8500 (bromine content 58% ( % By weight. The same applies hereinafter.) 1
9.7 parts was added and stirred to prepare a varnish for impregnation.
The bromine content is 9 relative to the total weight of the resin composition excluding the solvent.
%Met.

This varnish was impregnated in a glass cloth (7628 manufactured by Asahi Schwebel Co., Ltd.) and dried at 160 ° C. for 15 minutes to obtain a prepreg for lamination having a resin content of 45%.
Next, eight of these prepregs were sandwiched between copper foils having a thickness of 35 μm and pressure-molded at a pressing pressure of 30 kg / cm ^{2 at} 200 ° C. for 2 hours to obtain a copper-clad laminate having a thickness of 1.6 mm.
This laminated board was evaluated by the following tests. The results are shown in Table 2.

Combustion test: Conducted according to the method specified in UL Standard 94 of the United States, five test pieces were ignited twice, and the combustion time was measured 10 times in total, and the average value was obtained. Copper foil peeling strength: JIS C 6481 Copper foil peeling strength after heating: A test piece was exposed to 250 ° C. for 1 hour in a hot air circulation furnace in a nitrogen atmosphere, and then evaluated in the same manner as described above. .. Solder heat resistance test after boiling: The test piece is left in boiling water for 10 hours and then immersed in a solder bath at 280 ° C. for 1 minute. Dielectric constant: Q meter method Dielectric loss tangent: Q meter method

(Example 2 and Comparative Example 1) A laminated board was obtained from the composition shown in Table 1 by the same method as in Example 1. The same evaluation as in Example 1 was performed on the obtained copper-clad laminate. The results are shown in Table 2.

(Example 3) 48 parts of 3,3'-dimethallyl-bisphenol A (parts by weight; the same applies hereinafter), N, N '
52- (methylenedi-p-phenylene) dimaleimide
Parts and 43 parts of N-methyl-2-pyrrolidone as a solvent were stirred at 150 ° C. for 1.5 hours to obtain a mixture, and 81 parts of methyl ethyl ketone and β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane ( Nippon Unicar Co., Ltd .: A-186) 5 parts and brominated polycarbonate (Teijin Kasei Co., Ltd .: Fireguard 8500) 1
9.3 parts was added and stirred to prepare a varnish for impregnation.

A glass cloth (7628 manufactured by Asahi Schwabel Co., Ltd.) was impregnated with this varnish and dried at 160 ° C. for 15 minutes to obtain a prepreg for lamination having a resin content of 45%.
Next, 8 pieces of this prepreg were sandwiched by a copper foil having a thickness of 35 μm, and at a pressing pressure of 30 kg / cm ² , 220 ° C. and 30
After pressurizing for a minute, remove from the press machine and further 250 ℃
After curing in a hot air circulation oven for 1 hour at a thickness of 1.6 mm
A copper clad laminate of was obtained. The same evaluation as in Example 1 was performed on this laminated plate. The results are shown in Table 2.

(Example 4 and Comparative Example 2) A laminated board was obtained from the composition shown in Table 1 by the same method as in Example 3. The same evaluation as in Example 1 was performed on the obtained copper-clad laminate. The results are shown in Table 2.

(Comparative Example 3) 48 parts of 3,3'-dimethallyl-bisphenol A, 52 parts of N, N '-(methylenedi-p-phenylene) dimaleimide and 43 parts of N-methyl-2-pyrrolidone as a solvent, 150 parts of The mixture obtained by stirring for 1.5 hours at ℃, brominated epoxy resin varnish (Dainippon Ink and Chemicals, Inc .: Epicron 153-60
M (60% solid content, bromine content is 48% solid content)) 4
1 part, methyl ethyl ketone 89 parts, β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane (manufactured by Nippon Unicar Co., Ltd .: A-186) 5 parts, 2,5-dimethyl-2,5-di (t). -Butylperoxy) -3-hexyne (Nippon Yushi Co., Ltd .: Perhexin 25B) 2.5
And 0.2 parts of triphenylphosphine were added and stirred to prepare a varnish for impregnation. A laminated board was obtained from this varnish in the same manner as in Example 1. The same evaluation as in Example 1 was performed on the obtained copper-clad laminate. The results are shown in Table 2.

[0036]

[Table 1]

[0037]

[Table 2]

From the comparison of each Example in Table 2 with Comparative Examples 1 and 2, the flame retardant effect of the addition of (C) can be seen. Comparative Example 3 has a sufficient flame retardant effect, but has poor adhesiveness with a copper foil and solder heat resistance and cannot be used practically, and the electrical properties are deteriorated as compared with Example 1 having almost the same composition other than bromide. Seen.

[0039]

The resin composition of the present invention has excellent flame retardancy, and the physical properties of the resulting cured product are heat resistance, water resistance,
It has excellent electrical properties such as adhesion to metals and dielectric constant. INDUSTRIAL APPLICABILITY The resin composition of the present invention is extremely useful as a curable resin composition for a copper clad laminate.

Claims (1)

[Claims] 1. The following (A) is 20 to 80 parts by weight, and the following (B) is 80 to 20 parts by weight (where (A) + (B) = 1.
00 parts by weight) and the following (C). (A): A maleimide compound having a group represented by the following formula (i). [Chemical 1] (B): An alkenylphenol compound represented by the following formula (ii). [Chemical 2] (C): bromine-containing polycarbonate.