JP3290243B2 - Low dielectric constant thermosetting resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition having a low dielectric constant, a low dielectric loss tangent, excellent adhesion to metal, high heat resistance, and flame retardancy. Board,
It is suitably used for metal foil clad laminates and the like.

[0002]

2. Description of the Related Art In recent years, there has been a demand for a resin for a laminate having excellent heat resistance, a low dielectric constant, and a low dielectric loss tangent for a printed wiring used in a high frequency range. On the other hand, thermoplastic resins such as fluororesins and polyphenylene ether resins having a small dielectric constant have been proposed, but have problems such as poor workability and adhesiveness and lack of reliability. Therefore, an epoxy-modified polyphenylene ether resin or a polyphenylene ether-modified epoxy resin has been proposed for the purpose of improving workability and adhesiveness. However, the dielectric constant of the epoxy resin is high and satisfactory characteristics have not been obtained. A curable resin composition prepared by blending a polyphenylene ether resin and a polyfunctional cyanate ester resin, and further mixing other resins, adding a radical polymerization initiator, and performing a preliminary reaction (Japanese Patent Application Laid-Open No. 57-185350) ) Is known, but the decrease in the dielectric constant was insufficient.

Further, polybutadiene containing thermosetting 1,2-polybutadiene as a main component has a low dielectric constant, but has poor adhesiveness and insufficient heat resistance. Polyphenylene ether
A composition comprising 5 to 20 parts by weight of 1,2-polybutadiene, 5 to 10 parts by weight of a crosslinkable monomer and a radical crosslinking agent per 100 parts by weight (see JP-A-61-83224) is known. When 1,2-polybutadiene having a molecular weight of several thousand is used, stickiness remains when the solvent is removed from the composition, and the prepreg obtained by coating and impregnating on a glass substrate cannot maintain a tack-free state. Therefore, there was a practical problem. On the other hand, in order to eliminate stickiness, there is a method using 1,2-polybutadiene having a high molecular weight.However, according to this method, the solubility in a solvent is reduced, the solution has a high viscosity, and the fluidity is reduced, which is a practical problem. Was.

[0004]

SUMMARY OF THE INVENTION The present invention has been the result of intensive studies to obtain a thermosetting resin having low dielectric constant, low dielectric loss tangent, high heat resistance, high adhesiveness and excellent flame retardancy. It was done.

[0005]

According to the present invention, there is provided a compound represented by the general formula (1):
And / or a prepolymer (a) thereof, a bismaleimide compound and / or its prepolymer (b) represented by the general formula (2), and bromine having a structural unit represented by the general formula (3) Maleimide oligomer (c), wherein the weight ratio of (a) and (b) is 99%
Low dielectric constant thermosetting resin composition, wherein (c) is 50 to 200 parts by weight with respect to 100 parts by weight of the total of (a) and (b). Things.

[0006]

Embedded image (R _{1 to} R ₈ represent hydrogen or an alkyl group, which may be the same or different, R ₉ represents a divalent aliphatic residue, and has a carbon number of R _{1 to} R ₉ The total is 9 or more.)

Embedded image (R _{10 to} R ₁₇ each represent hydrogen or an alkyl group, which may be the same or different, R ₁₈ represents a divalent aliphatic residue, and has the same number of carbon atoms as R _{10 to} R ₁₈ The total is 9 or more.)

Embedded image (R and R 'each represent a divalent aliphatic and / or aromatic residue and may be the same or different.)

[0007]

The cyanate ester compound represented by the general formula (1) and / or a prepolymer thereof used in the present invention means an organic compound having two or more cyanate ester groups in a molecule. In the present invention, the polyfunctional cyanate ester itself or a prepolymer derived therefrom can be used. These compounds, if necessary, may be zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octylate,
By using a catalyst such as tin octylate, lead acetylacetonate, dibutyltin maleate or the like, the cyanate ester group can be trimerized and the reaction can be appropriately adjusted to form a prepolymer. The cyanate ester group can form a sym-triazine ring in the molecule by trimerization, and can be finally heat-cured.

In the formula (1), the substituents of R _{1 to} R ₈ represent hydrogen or an alkyl group, and R ₉ represents a divalent aliphatic residue. Further, the total number of carbon atoms of the alkyl substituents of R _{1 to} R ₉ is preferably 9 or more. When the carbon number is 9 or more, the free volume can be increased in the heat-cured structure, and the dielectric constant and the dielectric loss tangent can be reduced, which is preferable. If the total number of carbon atoms is less than 9, the dielectric constant and the dielectric loss tangent are not sufficiently reduced, which is not preferable.

The cyanate ester compound used in the present invention is not particularly limited as long as it is represented by the general formula (1), but specific examples include 2,2-bis (4-cyanate). Phenyl) nonane, 2,2-bis (3-tert-butyl-4-cyanatophenyl) propane, 2,2-bis (3-secondarybutyl-4-cyanatophenyl) propane, 1,1-bis (4 -Cyanatophenyl) decane, 1,1-bis (2-methyl-4-cyanato-5-tert-butylphenyl) -2-methyl-propane, 4,4'-cyclohexylidene-
Bis [2- (1,1-dimethylethyl) cyanatobenzene], 4,
4'-methylene-bis [2,6-bis (1,1-dimethylethyl) cyanatobenzene], 4,4'-methylene-bis [2,6-di-secondary-butylcyanatobenzene], 4,4 '-Cyclohexylidene-bis (2-cyclohexyl-1-cyanatobenzene), 4,4'-methylene-bis (2-nonyl-cyanatobenzene), 4,4'-(1-methylethylidene) bis [ 2,6-bis (1,1-dimethylethyl) cyanatobenzene], 4,4 '-(2-ethylhexylidene) biscyanatobenzene, 4,4'-(1-methylheptylidene) bis Cyanate benzene, 4,4'-cyclohexylidene-bis (3-methyl-cyanatobenzene) and the like.

The bismaleimide compound represented by the general formula (2) used in the present invention is obtained by further dehydrating and ring-closing a bismaleamic acid obtained by reacting maleic anhydride and a diamine. This bismaleimide is
Furthermore, with polyfunctional amines and polyfunctional allylphenol compounds
It is possible to obtain a prepolymer by reacting at a temperature of 200 ° C. or less. The bismaleimide and / or its prepolymer obtained in this way has excellent heat resistance, and it is of course possible to use two or more kinds in combination.

The substituent of R _{10 to} R ₁₇ in the formula (2) is
R ₁₈ represents a hydrogen or alkyl group, and R ₁₈ represents a divalent aliphatic residue. Further, the total number of all carbon atoms of the alkyl substituents of R _{10 to} R ₁₈ is preferably 9 or more. When the carbon number is 9 or more, the free volume can be increased in the heat-cured structure, and the dielectric constant and the dielectric loss tangent can be reduced, which is preferable. If the total number of carbon atoms is less than 9, the dielectric constant and the dielectric loss tangent are not sufficiently reduced, which is not preferable.

The bismaleimide compound used in the present invention is not particularly limited as long as it is represented by the general formula (2).
[4- (4-maleimidophenoxy) phenyl] nonane, 2,2-bis [3-tert-butyl-4- (4-maleimidophenoxy)
Phenyl] propane, 2,2-bis [3-secondary butyl-4
-(4-maleimidophenoxy) phenyl] propane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] decane, 1,1-
Bis [2-methyl-4- (4-maleimidophenoxy) -5-tert-butylphenyl] -2-methylpropane, 4,4'-cyclohexylidene-bis [1- (4-maleimidophenoxy) -2-
(1,1-dimethylethyl) benzene], 4,4'-methylene-bis
[1- (4-maleimidophenoxy) -2,6-bis (1,1-dimethylethyl) benzene], 4,4'-methylene-bis [1- (4-maleimidophenoxy) -2,6-di- Secondary butylbenzene],
4,4′-cyclohexylidene-bis [1- (4-maleimidophenoxy) -2-cyclohexylbenzene], 4,4′-methylene-bis [1- (maleimidophenoxy) -2-nonylbenzene], 4,
4 '-(1-methylethylidene) -bis [1- (maleimidophenoxy) -2,6-bis (1,1-dimethylethyl) benzene, 4,4'-(2-
Ethylhexylidene) -bis [1- (maleimidophenoxy)-
Benzene], 4,4 '-(1-methylheptylidene) -bis [1- (maleimidophenoxy) -benzene], 4,4'-cyclohexylidene-bis [1- (maleimidophenoxy) -3-methyl Benzene].

The brominated maleimide oligomer represented by the general formula (3) used in the present invention can be obtained by a Michael addition reaction of a bismaleimide obtained by reacting maleic anhydride with a diamine and a brominated aromatic diamine. it can. Further, it can also be obtained by brominating an oligomer produced by a Michael addition reaction of bismaleimide and an aromatic diamine. The brominated maleimide oligomer thus obtained has both the inherent heat resistance of the maleimide resin and the effect of imparting flame retardancy by bromine atoms.

The low dielectric constant thermosetting resin composition of the present invention comprises:
It comprises a cyanate ester compound and / or a prepolymer thereof as the component (a), a bismaleimide compound and / or a prepolymer thereof as the component (b), and a brominated maleimide oligomer as the component (c). a),
The weight ratio of (b) and (c) is such that (a) and (b) are 99/1 to 1/1.
(C) is preferably 50 to 200 parts by weight with respect to 100 parts by weight in total of (a) and (b). Even when the components (a) and (b) are formed into the composition at the above-described mixing ratio, the dielectric properties of the cured product are improved as compared with the cured products of the components (a) and (b) alone. In other words, the combined use of the components (a) and (b) is characterized in that a value smaller than the dielectric constant and the dielectric loss tangent of each of the cured products can be obtained. Also, component (a),
It is preferable that the compounding amount of the component (c) is 50 to 200 parts by weight with respect to 100 parts by weight of the total of (b). If the amount is less than 50 parts by weight, the flame-retardant effect becomes poor. It is not preferable because the heat resistance decreases.

In the resin composition of the present invention, it is of course possible to add a thermosetting resin or a thermoplastic resin other than the components (a), (b) and (c) as long as the original properties are not impaired. It is. If necessary, a release agent, a coloring agent, a flame retardant aid, a coupling agent, various fillers, and the like can be added.

Although the resin composition of the present invention is used in various forms, a solvent is often used when coating and impregnating a substrate. The solvent used must have good solubility in part or all of the composition, but a poor solvent can be used as long as it does not adversely affect the composition. Examples of the solvent used include acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as cyclohexanone, aromatic hydrocarbon solvents such as toluene, xylene and mesitylene, methyl cellosolve, ethyl cellosolve, butyl cellosolve, isobutyl cellosolve, diethylene glycol. Various types of monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, etc. Glycol ether solvent Solvent acetate, ethyl cellosolve acetate, butyl cellosolve acetate, ester solvents such as ethyl acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dialkyl glycol ether solvents such as diethylene glycol dibutyl ether, N, N-dimethylacetamide, N, N -There are amide solvents such as dimethylformamide and N-methyl-2-pyrrolidone, and alcohol solvents such as methanol and ethanol, and some of these can be used in combination.

The varnish obtained by dissolving the resin composition of the present invention in the above-mentioned solvent may be a woven glass cloth, a nonwoven glass cloth or paper,
Alternatively, a prepreg for a printed wiring board can be obtained by applying and impregnating a substrate such as a cloth containing a component other than glass and drying it in a drying oven at a temperature in the range of 80 to 200 ° C. The prepreg is used for producing a printed wiring board by heating and pressing, and the resin composition of the present invention has a low dielectric constant, a low dielectric loss tangent, excellent workability, excellent adhesiveness to metal, high heat resistance, and It is a flame-retardant thermosetting resin having excellent chemical resistance, and is suitably used for laminates, metal-clad laminates and the like.

[0018]

The present invention will be described below in more detail with reference to examples.

(Synthesis Example 1) Synthesis of brominated maleimide oligomer A 2,4-bis [4- (4-maleimidophenoxy) phenyl) was placed in a four-necked 3-liter separable flask equipped with a stirrer, a thermometer, and a reflux condenser. ] Propane 538 g, 2,2-bis [4- (4-amino-3,
After charging 683 g of [5-dibromophenoxy) phenyl] propane, the system was heated using an oil bath so that the temperature in the system became 150 ° C. The system was maintained at 150 ° C., and stirring was continued. After 60 minutes, the oil bath was removed, and the contents were taken out of the system and cooled. The molecular weight of the obtained brominated maleimide oligomer is represented by G
It was about 2600 when measured by PC. Further, the odor composition content was measured and found to be 28% by weight.

(Synthesis Example 2) Synthesis of Brominated Maleimide Oligomer 2,2-Bis [4- (4-) was placed in a four-necked 3-l separable flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel. 538 g of maleimidophenoxy) phenyl] propane, 2,2-bis [4- (4-
After 386 g of [aminophenoxy) phenyl] propane was charged, the system was heated using an oil bath so that the temperature in the system became 150 ° C. The system was maintained at 150 ° C., and stirring was continued. After 45 minutes, the oil bath was removed, and the contents were taken out of the system and cooled.
The molecular weight of the maleimide oligomer obtained by sampling was 3,200 as measured by GPC.

Further, 800 ml of dioxane was added to the flask.
g to dissolve the maleimide oligomer.
g of bromine and 320 g of bromine are added dropwise at room temperature with stirring. After stirring at room temperature for 8 hours, the mixture was washed with water and a 10% aqueous solution of NaOH, and dioxane was evaporated using an evaporator to obtain a target brominated maleimide oligomer. When the bromine content of the obtained maleimide oligomer was measured, it was 36% by weight.

Example 1 4,4 '-(2-methylpropylidene) bis [1- (4-maleimidophenoxy) -3-methyl-6- (1,1
-Dimethylethyl) benzene] 300 g, 4,4′-cyclohexylidene-bis [2- (1,1-dimethylethyl) cyanatobenzene] 200 g, and brominated maleimide oligomer 500 g obtained in Synthesis Example 1 A mixed solvent of formamide / methyl ethyl ketone 1/1 was added and dissolved, and the non-volatile content was 50%.
% Of the varnish solution was adjusted. Triferylphosphine was gradually added to this solution to adjust the gel time on a hot plate at 170 ° C. to 4 minutes ± 15 seconds.

Thereafter, 50 parts by weight of a glass cloth (0.18 mm in thickness, E-glass manufactured by Nitto Boseki Co., Ltd.) was impregnated with 50 parts by weight of the varnish with a solid content using the varnish, and the varnish was dried in a drying oven at 150 ° C. After drying for 4 minutes, a prepreg was prepared. The obtained prepreg was tack-free and excellent in workability. Eight pieces of the dried prepregs were stacked, and an electrolytic copper foil having a thickness of 35 μm was stacked on the upper and lower sides, and heated and pressed at a pressure of 40 kgf / cm ² and a temperature of 180 ° C. for 120 minutes to obtain a laminate having a thickness of 1.6 mm. . After the surface copper foil of the laminate was removed by etching, the laminate was treated at 121 ° C. under a pressure cooker under a pressure of 2.0 atm for 20 hours, and the weight increase was measured. The same test piece was immersed in methylene chloride for 10 minutes at room temperature, and the appearance was checked to determine the solvent resistance. Table 2 shows the results.

The measurement of the dielectric constant and the dielectric loss tangent are performed according to JIS C 6481.
The capacitance was measured at a frequency of 1 MHz. JIS C 648 for solder heat resistance and peel strength
The solder heat resistance was measured at 260 ° C. for 300 seconds to check for any abnormal appearance. Flame retardancy was evaluated by the vertical method according to UL-94 standard. The glass transition temperature was determined from the peak temperature of tan δ by the viscoelastic method. Further, the coefficient of linear expansion in the thickness direction of the obtained laminate was measured by thermomechanical analysis. Table 2 shows the results together.

(Examples 2 to 4 and Comparative Examples 1 to 4) Laminates were manufactured in the same manner as in Example 1 except that the formulation was as shown in Table 1 and the results are shown in Table 2. .

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

As is clear from the results shown in Tables 1 and 2, the resin composition of the present invention has a low dielectric constant and a low dielectric loss tangent, and has excellent adhesiveness to metal, heat resistance and chemical resistance. It is a flame-retardant thermosetting resin composition. Therefore, it is the most suitable resin for printed wiring boards that require low dielectric constant and low dielectric loss tangent, and copper-clad laminates can be manufactured in the same process as conventional resin for laminates, which is an industrial advantage. Is big.

Continuation of front page (56) References JP-A-56-93735 (JP, A) JP-A-56-104962 (JP, A) JP-A-3-88810 (JP, A) JP-A-6-306165 (JP) JP-A-6-306166 (JP, A) JP-A-6-306167 (JP, A) JP-A-6-306168 (JP, A) JP-A-6-322119 (JP, A) 6-322269 (JP, A) JP-A-3-265630 (JP, A) JP-A-6-100508 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 73/00 -73/26 CAPLUS (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A cyanate ester compound represented by the general formula (1) and / or a prepolymer (a) thereof, a bismaleimide compound represented by the general formula (2) and / or a prepolymer thereof (b), a general formula ( A brominated maleimide oligomer (c) having a structural unit represented by 3),
(A), the weight ratio of (b) is in the range of 99/1 to 1/99,
(C) is 50 to 2 with respect to a total of 100 parts by weight of (a) and (b).
A thermosetting resin composition having a low dielectric constant, which is 100 parts by weight. Embedded image (R _{1 to} R ₈ represent hydrogen or an alkyl group, which may be the same or different, R ₉ represents a divalent aliphatic residue, and has a carbon number of R _{1 to} R ₉ The total is 9 or more.) (R _{10 to} R ₁₇ each represent hydrogen or an alkyl group, which may be the same or different, R ₁₈ represents a divalent aliphatic residue, and has the same number of carbon atoms as R _{10 to} R ₁₈ The total is 9 or more.) (R and R 'each represent a divalent aliphatic and / or aromatic residue and may be the same or different.)