JPH06136266A - Flame-retardant and heat-resistant resin composition having excellent fluidity - Google Patents

Abstract

PURPOSE:To provide a polyimide resin composition having excellent flame retardancy as well as fluidity and suitable for printed circuit board for electronic equipment required to have lower dielectric constant. CONSTITUTION:The flame-retardant and heat-resistant resin composition having excellent fluidity is produced by compounding (A) a heat-resistant resin composition produced by the thermal reaction of a maleimide compound having at least two maleimide groups with a diamine compound with (B) a compound containing halogen atom and having a melting point of 50-130 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant heat-resistant resin composition having excellent fluidity, which is a polyimide-based resin used for a printed wiring board for electronic equipment which requires a low dielectric constant.

[0002]

2. Description of the Related Art In printed wiring boards for electronic devices, glass cloth epoxy resin laminates using epoxy resin as a binder have been widely used, and it is necessary to make the substrates flame-retardant for safety against fire. Further, in order to cope with the miniaturization of electronic parts and the high density of wiring, it is required to improve the heat resistance of the printed wiring board.

Polyamino bismaleimide obtained by reacting bismaleimide with diamine by heating has heat resistance superior to that of epoxy resin. For example, kelimide 60
A printed wiring board using 1 (product name of Rhone-Poulin) has been developed.

However, the flame retardancy of Kelimide 601 is UL94 standard V-1, and in order to achieve V-0, flame retardation by some method is required. In addition, the polyamino bismaleimide has a problem that the inherent melt viscosity of the resin is higher than that of the epoxy resin, so that the fluidity is poor and the dimensional stability is poor at the time of molding a multi-layer board. Is being done.

In recent years, in order to improve the data processing speed,
It has become necessary to reduce the dielectric constant of resin for substrates. Therefore, for the purpose of lowering the dielectric constant of the polyamino bismaleimide resin composition, it has been attempted to apply a bismaleimide compound containing a fluorine atom to a resin for a substrate of a printed wiring board, but a bismaleimide compound containing a fluorine atom is used. It has not been put to practical use because it is expensive. On the other hand, JP-A-3-1483
As disclosed in Japanese Patent Laid-Open No. 6-2898 and Japanese Patent Laid-Open No. 2-298548, a polyamino bismaleimide resin composition having a low dielectric constant can be obtained by increasing the hydrocarbon ratio by using an alkylene bond type bismaleimide compound and a diamine compound. There is a way to make it. However, in this alkylene-bonded polyaminobismaleimide, flame retardance is indispensable because the composition ratio of the alkylene group, which is a combustible component, increases.

As a method for making a polyimide resin composition such as polyaminomaleimide flame-retardant, various methods of mixing or reacting a compound containing a bromine atom have been conventionally proposed. For example, an acrylate compound of tetrabromobisphenol A disclosed in Japanese Patent Publication No. 1-48298, an alkylenebistetrabromophthalimide compound disclosed in Japanese Patent Publication No. 63-10178,
There is a method using tribromophenylmaleimide disclosed in JP-A-3-131629. As a method of using other compounds, JP-A-1-113342
There is a method using a cyclic phosphonitrile disclosed in Japanese Patent Laid-Open No.

[0007]

[Patent Document 1] Japanese Patent Application Laid-Open No. 3-14836
In the polyamino bismaleimide using the alkylene bond type bismaleimide compound and the diamine compound disclosed in JP-A No. 2-298548 and JP-A No. 2-298548, the dielectric constant of the resin composition can be lowered, but the flame retardancy is low. Was insufficient. Further, it is necessary to improve the fluidity, which was a drawback of the conventional polyamino bismaleimide,
Improving the fluidity of the resin by modifying the epoxy resin or the like is not desirable because it increases the dielectric constant.

In the conventional flame retardant method, the phosphorus-based flame retardant is
There is a problem that the flame retardant effect is small for a compound having a small oxygen atom content such as an alkylene-bonded polyaminomaleimide resin composition. Further, an acrylate compound of tetrabromobisphenol A disclosed in JP-B-1-48298 and JP-B-63-1
In the method using an alkylenebistetrabromophthalimide compound disclosed in JP-A No. 0178, although flame retardancy can be imparted by incorporating a bromine-containing atom, the melting point of these bromine compounds is as high as 160 ° C. or higher. Therefore, the effect of improving the fluidity of the resin was not recognized, and therefore, the modification of the epoxy resin or the like was required, which was unsuitable as a flame retardant method for the low dielectric constant resin composition. Further, in the method using tribromophenylmaleimide disclosed in JP-A-3-131629, the maleimide group reacts with the amino group remaining in the polyaminobismaleimide, so that the melt viscosity is increased and the fluidity is improved. There was a problem that I could not do it.

The present invention provides a resin composition suitable for a printed wiring board for electronic equipment which requires a low dielectric constant, and a polyimide resin composition having excellent flame retardancy and fluidity. is there.

[0010]

That is, according to the present invention, a heat-resistant resin composition obtained by heating a maleimide compound having at least two maleimide groups and a diamine compound contains a halogen atom and has a melting point of 50. ~ 13
It is intended to provide a flame-retardant heat-resistant resin composition having excellent fluidity, which is characterized by containing a compound at 0 ° C.

In the resin composition of the present invention, all or part of the maleimide compound has the general formula [I].

[0012]

[Chemical 3] (In the formula, R _{1 to} R ₆ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least one of R _{1 to} R ₆ has 1 carbon atom.
To 4 alkyl groups, which may be the same or different from each other. n shows the integer of 1-3. It is preferable to use an alkylene bond type bismaleimide compound represented by the formula (1).

The diamine compound may be wholly or partly represented by the general formula [II]

[0014]

[Chemical 4] (In the formula, R _{1 to} R ₆ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least one of R _{1 to} R ₆ has 1 carbon atom.
To 4 alkyl groups, which may be the same or different from each other. n shows the integer of 1-3. It is preferable to use an alkylene-bonded aromatic diamine represented by

Specific examples of the alkylene bond type bismaleimide compound represented by the general formula [I] include 3,3 ',
5,5'-tetramethyl-4,4'-bismaleimidodiphenylmethane, 3,3 ', 5,5'-tetraethyl-
4,4'-bismaleimidodiphenylmethane, 3,
3 ', 5,5'-tetraisopropyl-4,4'-bismaleimidodiphenylmethane, 2,2-bis (3,4'
-Maleimidophenyl) propane, α, α'-bis (4
-Maleimidophenyl) -m-diisopropylbenzene, α, α'-bis (4-maleimidophenyl) -p-
Diisopropylbenzene and α, α′-bis (3,5-
Dimethyl-4-maleimidophenyl) -p-diisopropylbenzene and the like can be mentioned.

As the other maleimide compound having at least two maleimide groups used together with the alkylene-bonded bismaleimide compound represented by the general formula [I], an aromatic bis derivative derived from an aromatic diamine can be used. Examples thereof include maleimide and polyamine compounds, and polymaleimide compounds obtained by maleating an aniline-formaldehyde resin. Specific examples of the aromatic bismaleimide include paraphenylene bismaleimide, 4,4'-bismaleimide diphenylmethane, 4,4'-bismaleimide diphenyl ether, 4,4'-bismaleimide diphenyl sulfone, xylylene bismaleimide, and 2. 2-
Examples include bis [4- (4-maleimidophenoxy) phenyl] propane and 2,2-bis [4- (3-maleimidophenoxy) phenyl] propane.

When the alkylene-bonded bismaleimide compound represented by the general formula [I] is used, the resin composition has a low dielectric constant and is suitable for a printed wiring board of electronic equipment such as a computer. In order to obtain a flame-retardant low dielectric constant resin composition having a low dielectric constant and excellent fluidity according to the present invention, it is necessary to use as many alkylene-bonded bismaleimide compounds represented by the general formula [I] as possible. It is preferable to use at least 50% by weight based on at least all maleimide compounds.

Specific examples of the alkylene-bonded aromatic diamine represented by the general formula [II] include 3,3 ',
5,5'-tetramethyl-4,4'-diaminophenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'
-Diaminodiphenylmethane, 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane, 2,2-bis (3,4'-aminophenyl) propane, α, α'-bis (4- Aminophenyl) -m-diisopropylbenzene, α, α′-bis (4-aminophenyl) -p-diisopropylbenzene and α, α′-bis (3,5-dimethyl-4-aminophenyl) -p-diisopropylbenzene Etc.

As the other diamine compound used together with the alkylene-bonded diamine compound represented by the general formula [II], aromatic diamine is preferably used in consideration of heat resistance. Specific examples of the aromatic diamine compound include phenylenediamine, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy). ) Phenyl] sulfone.

When the alkylene-bonded aromatic diamine compound represented by the general formula [II] is used, the resin composition has a low dielectric constant and is suitable for a printed wiring board of electronic equipment such as a computer. In order to obtain a flame-retardant low dielectric constant resin composition having a low dielectric constant and excellent fluidity according to the present invention, it is necessary to use as many alkylene-bonded aromatic diamine compounds represented by the general formula [II] as possible. However, it is preferable to use 50% by weight or more based on at least all amine compounds.

The heat-resistant resin composition used in the present invention comprises an alkylene-bonded bismaleimide compound represented by the general formula [I] having at least two maleimide groups and another maleimide compound and the general formula [II]. The alkylene-bonded aromatic diamine and the other diamine compound represented by are dissolved both in a solvent-free or a suitable solvent, and a catalyst-free or a catalyst is preferably added.
It is obtained by heating the reaction at 130 ° C.

Examples of the catalyst include basic catalysts such as alkali hydroxides, metal alkalis, alkoxides, pyridine, and imidazoles such as 2-ethyl-4-methylimidazole. The catalyst is preferably added in an amount of 0.01 to 10% by weight based on the resin composition.

As the reaction solvent, a polar solvent such as dimethylformamide, various cellosolves or propylene glycol monomethyl ether (PGM) can be used.

In the present invention, by adding a compound containing a halogen atom and having a melting point of 50 to 130 ° C., it is possible to impart flame retardancy to the above heat resistant resin composition and improve its fluidity. it can. In order to make the properties of the flame-retarded low dielectric constant resin composition more preferable, the compound containing a halogen atom used in the present invention is a reaction of an acryloyl group, a methacryloyl group, an amino group or the like as exemplified below. A compound having a functional group is desirable. That is, tribromophenyl acrylate (melting point 75 ° C.), tribromophenyl methacrylate (melting point 6
5 ° C.), acrylic acid ester of tribromophenol-ethylene oxide adduct (melting point 56 ° C.), methacrylic acid ester of tribromophenol-ethylene oxide adduct (melting point 92 ° C.), tetrabromobisphenol A-
Acrylic ester of ethylene oxide adduct (melting point 1
30 ° C.), methacrylic acid ester of tetrabromobisphenol A-ethylene oxide adduct (melting point 72 ° C.), and other acrylic acid esters or methacrylic acid esters of brominated phenols. There are also brominated aromatic amine compounds such as tribromoaniline (melting point 121 ° C.).

In the present invention, the compound containing a halogen atom is 5
It is important to have a relatively low melting point of 0 to 130 ° C, and even a compound having a similar reactive group and a similar structure, for example, a methacrylic acid ester of tetrabromobisphenol A (melting point 160 ° C), etc. Although flame retardancy can be imparted, it cannot improve the fluidity of the resin composition and cannot be used as the flame retardant of the present invention.

The compound containing a halogen atom may be added to and mixed with a heat-resistant resin composition obtained by heating and reacting a maleimide compound having at least two maleimide groups with a diamine compound. Alternatively, they may be mixed by heating if necessary. In addition, when the maleimide compound having at least two maleimide groups and the diamine compound are heated and reacted, a compound containing a halogen atom which is a flame retardant component may be added and heated to be blended in the heat resistant resin composition. . At this time, the entire amount of the compound containing a halogen atom may be reacted by heating, or a part thereof may be reacted by heating and the rest may be mixed with the heat resistant resin composition obtained after the heating reaction to form a resin composition.

The compounding amount of the compound containing a halogen atom, which is a flame retardant component, varies depending on the degree of flammability of the flame-retarded resin composition, but the content of halogen atom is preferably 100 parts by weight of the resin composition. Is used in an amount of 0.1 to 30 parts by weight.

In the flame-retardant heat-resistant resin composition having excellent fluidity of the present invention, an anionic polymerization initiator or an organic oxide is used as a curing catalyst, if necessary. As the anionic polymerization initiator, 2-methylimidazole, 2-ethyl-4
-Imidazoles such as -methylimidazole and 2-phenylimidazole, benzyldimethylamine, triethylenediamine, DBU (1,8-diazabicyclo (5,5)
4,0) Undecene-7) and other amines, dicyandiamide, triphenylphosphine, organometallic compounds and the like, which are preferably added in an amount of 0.1 to 10% by weight based on the resin composition. Examples of the organic peroxide include benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, t-butyl perbenzoate and the like, and preferably 0.1 to 10 relative to the resin composition.
Wt% is added.

The flame-retardant heat-resistant resin composition having excellent fluidity of the present invention has the following properties as long as its dielectric constant is not increased.
Unsaturated polyester, triallyl isocyanurate, and / or diallyl phthalate resin can be appropriately combined and used.

When a prepreg for printed wiring boards and a laminated board are produced using the flame-retardant heat-resistant resin composition of the present invention having excellent fluidity, the flame-retardant resin composition is dissolved in an appropriate organic solvent. Further, if necessary, an anionic polymerization initiator, an organic peroxide or the like is added as a curing catalyst to obtain an impregnating varnish. Further, additives such as a filler can be used in combination, if necessary. Then, this varnish is impregnated into glass fiber or the like and dried to form a prepreg sheet, and several prepreg sheets are stacked and laminated at a predetermined temperature and pressure to form a laminated plate.

[0031]

According to the present invention, a heat-resistant resin composition obtained by reacting a maleimide compound having at least two maleimide groups with a diamine compound by heating is a compound containing a halogen atom and having a melting point of 50 to 130 ° C. By blending it, flame retardancy is imparted and fluidity is improved, and an alkylene bond-type bismaleimide represented by the general formula [I] or the general formula [II] is added to all or part of the maleimide compound or the diamine compound. Alternatively, by using an alkylene-bonded aromatic diamine, the resin composition can have a low dielectric constant and flame retardancy. Moreover, in the method of flame retardation essential for the alkylene bond type resin composition,
By using a compound containing a halogen atom with a low melting point, the flame-retardant component melts during molding of the multilayer board and lowers the melt viscosity of the resin composition, so the flow of the resin is important for the production of high-quality multilayer printed wiring boards. The sex can be improved.
As a result, it is not necessary to modify with an epoxy resin to improve the fluidity, and it is possible to obtain a resin composition having both a low dielectric constant, flame retardancy and fluidity without increasing the dielectric constant. .

[0032]

EXAMPLES The present invention will now be described in detail based on examples, but the present invention is not limited thereto.

Examples 1 to 5 303 g of α, α'-bis (4-maleimidophenyl) -m-diisopropylbenzene and 36 g of 4,4'-bismaleimidediphenylmethane were used as maleimide compounds, and α, α'- was used as a diamine compound. 34 g of bis (4-aminophenyl) -m-diisopropylbenzene and 2,
Using 33 g of 2-bis [4- (4-aminophenoxy) phenyl] propane, these were dissolved in 300 g of N, N-dimethylformamide (hereinafter, DMF) and reacted at 120 ° C. for 1 hour. Then, the flame retardant of Table 1 was added in the blending amount shown in Table 1 and dissolved by stirring for 10 minutes. After cooling the reaction product to room temperature, 0.5% was added to the solvent-free resin composition.
Wt% 2-ethyl-4-methylimidazole and DMF
Was added to prepare a varnish having a resin content of 50% by weight.

This varnish was mixed with E glass cloth (0.1 mm
(Thickness, manufactured by Nitto Boseki), and then dried at 160 ° C. for 3 minutes to obtain a prepreg having a resin content of 45% by weight. A solid resin was collected from this prepreg, a viscosity change curve at 130 ° C was obtained using a flow tester manufactured by Shimadzu Corporation, and the minimum melt viscosity was measured. The results are shown in Table 1.

Also, using 16 sheets of prepreg, the prepreg is vertically
5μm electrolytic copper foil is overlaid, pressure 0.4MPa, temperature 20
Laminated and molded at 0 ° C for 2 hours, then 225
A post-curing treatment was performed at 4 ° C. for 4 hours to prepare a copper-clad laminate having a thickness of 1.6 mm. The dielectric constant, glass transition temperature Tg (TMA method) and flame retardancy (UL-94-vertical method) of this copper clad laminate were measured.

Comparative Example 1 Commercially available kelimide 601 (polyamino bismaleimide,
300 g of Rhone-Poulin brand name) was dissolved in DMF, and 5% by weight of 2-ethyl-4-methylimidazole was added to prepare an impregnating varnish having a resin content of 50% by weight. A prepreg was prepared according to the example, the minimum melt viscosity of the resin was measured, and then a copper clad laminate was prepared in the same manner, and its characteristics were measured. The results are shown in Table 1 and Table 2, respectively.

Comparative Examples 2-3 After synthesizing a heat resistant resin composition in the same manner as in Examples, 33 g of a compound containing a bromine atom shown in Table 1 was added and dissolved with stirring for 10 minutes. Thereafter, a varnish and a prepreg were prepared according to the examples, and the minimum melt viscosity of the resin was measured. The results are shown in Table 1.

Further, a copper clad laminate was prepared according to the examples, and the dielectric constant, glass transition temperature Tg (TMA method) and flame retardancy (UL-94-vertical method) were measured. The results are shown in Table 2.

From Table 1, it is clear that in Examples 1 to 5 using the compound containing a halogen atom specified by the present invention, the melt viscosity of the prepreg was low, and the fluidity which was a drawback of polyaminobismaleimide can be improved. It was Table 2
From this, it was confirmed that the laminated plates of Examples 1 to 5 had a low dielectric constant and had no problems in heat resistance (Tg) and flame retardancy.

[0040]

[Table 1] A: Trade name of Daiichi Kogyo Pharmaceutical, acrylic acid ester of tribromophenol ethylene oxide adduct B: 〃 tribromophenyl methacrylate C: 〃 tetrabromobisphenol A methacrylic acid ester of ethylene oxide adduct D: 〃 tribromophenyl acrylate E: Manac Company name, tribromoaniline F: Dai-ichi Kogyo Seiyaku brand name, methacrylic acid ester of tetrabromobisphenol A G: Cytex company name, alkylenebistetrabromophthalimide

[0041]

[Table 2]

[0042]

EFFECTS OF THE INVENTION According to the present invention, a heat-resistant resin composition in which an alkylene-bonded bismaleimide compound is used in all or part of the maleimide compound and an alkylene-bonded aromatic diamine is used in all or part of the diamine compound. By adding a compound containing a halogen atom to the product and having a melting point of 50 to 130 ° C., flame retardancy is imparted, fluidity, which was a conventional defect, is improved, and moreover, it is suitable for a printed wiring board for electronic devices. It is possible to obtain a resin composition having a low dielectric constant, which is of great industrial value.

Claims (8)

[Claims] 1. A heat-resistant resin composition obtained by heating a maleimide compound having at least two maleimide groups and a diamine compound by heating, and blending a compound containing a halogen atom and having a melting point of 50 to 130 ° C. A flame-retardant heat-resistant resin composition having excellent fluidity, which is characterized by the following. 2. All or part of the maleimide compound is represented by the general formula [I]: (In the formula, R _{1 to} R ₆ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least one of R _{1 to} R ₆ has 1 carbon atom.
To 4 alkyl groups, which may be the same or different from each other. n shows the integer of 1-3. The flame-retardant low dielectric constant resin composition having excellent fluidity according to claim 1, which is an alkylene bond type bismaleimide compound represented by the formula (1). 3. The diamine compound is wholly or partly represented by the general formula [II]: (In the formula, R _{1 to} R ₆ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least one of R _{1 to} R ₆ has 1 carbon atom.
To 4 alkyl groups, which may be the same or different from each other. n shows the integer of 1-3. 3. An alkylene-bonded aromatic diamine represented by
A flame-retardant heat-resistant resin composition having excellent fluidity as described. 4. The flame-retardant heat-resistant resin composition having excellent fluidity according to claim 1, 2 or 3, wherein the compound containing a halogen atom is a compound having an acryloyl group or a methacryloyl group. 5. The flame-retardant heat-resistant resin composition having excellent fluidity according to claim 1, 2 or 3, wherein the compound containing a halogen atom is a compound having an amino group. 6. A bromine-containing compound alone or 2 in which the compound containing a halogen atom is selected from acrylic acid esters or methacrylic acid esters of tribromophenol and acrylic acid esters or methacrylic acid esters of tribromophenol-ethylene oxide adducts. The flame-retardant heat-resistant resin composition having excellent fluidity according to claim 1, 2, 3 or 4, which is a mixture of two or more kinds. 7. The flame-retardant heat resistance with excellent fluidity according to claim 1, 2, 3 or 4, wherein the compound containing a halogen atom is an acrylic acid ester or a methacrylic acid ester of a tetrabromobisphenol A-ethylene oxide adduct. Resin composition. 8. The flame-retardant heat-resistant resin composition having excellent fluidity according to claim 1, 2, 3 or 5, wherein the compound containing a halogen atom is brominated aniline.