JPH06271778A - Thermosetting resin composition with flame retardancy and low permittivity - Google Patents

Abstract

PURPOSE:To obtain a resin composition which has a low permittivity, a low dielectric dissipation factor, is excellent in adherence to metals, flame retardancy, heat resistance, and chemical resistance, and is especially suited for use in a printed circuit board for which a low permittivity and a low dielectric dissipation factor are required. CONSTITUTION:This composition comprises 100 pts.wt. Br compound represented by the formula (wherein (l) is an integer of 0-5 and (m) is an integer of 2-5) and 100-900 pts.wt. thermosetting resin having a relative permittivity as measured at 1MHz of 3.2 or lower.

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, a high heat resistance and a flame retardant property, which is excellent in adhesiveness to a metal, and is laminated. Board,
It is preferably 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 laminated board which has excellent heat resistance, low dielectric constant and low dielectric loss tangent for printed wiring used in a high frequency region. On the other hand, a thermoplastic resin such as a fluororesin or a polyphenylene ether resin having a small dielectric constant has been proposed, but it has 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 epoxy resin has a high dielectric constant, and satisfactory characteristics have not been obtained. Curable resin composition obtained by blending a polyphenylene ether resin and a polyfunctional cyanate ester resin, and further other resins, adding a radical polymerization initiator, and preliminarily reacting them (JP-A-57-185350). However, the decrease in the dielectric constant was insufficient.

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
There is known a composition containing 5 to 20 parts by weight of 1,2-polybutadiene, 5 to 10 parts by weight of a crosslinkable monomer and 100 parts by weight of a radical crosslinking agent (see JP-A-61-83224). 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 a glass substrate etc. cannot maintain a tack-free state. So there was a problem in practice. On the other hand, there is a method of using a high molecular weight 1,2-polybutadiene to eliminate stickiness, but this method has a practical problem because the solubility in a solvent is lowered, the solution becomes highly viscous and the fluidity is lowered. It was

[0004]

DISCLOSURE OF THE INVENTION The present invention is earnestly studied in order to obtain a thermosetting resin which is flame-retardant and has low dielectric constant, low dielectric loss tangent, high heat resistance, high adhesiveness and excellent workability. It was made as a result of repeating.

[0005]

The present invention is based on the general formula (1)
100 parts by weight of the Br compound shown by 100 to 90 having a relative dielectric constant of 3.2 or less when measured at 1 MHz.
A flame-retardant low dielectric constant thermosetting resin composition consisting of 0 parts by weight.

[Chemical 1]

[0006]

The Br compound represented by the general formula (1) used in the present invention essentially functions as a flame retardant. Generally, the flame retardant has a tendency to decrease the dielectric properties with an increase in the addition amount thereof, but the compound represented by the general formula (1) used in the present invention has a characteristic that its adverse effect is extremely small. It is a compound that is very suitable for achieving both dielectric properties and flame retardancy. Further, the flame retardant low dielectric constant thermosetting resin composition of the present invention can be obtained by combining the Br compound and the low dielectric constant thermosetting resin component.

The thermosetting resin component used in the present invention is required to have a relative dielectric constant value of 3.2 or less measured at 1 MHz. When it exceeds 3.2, when the resin composition obtained from the Br compound represented by the general formula (1) is used to form a laminate with a general-purpose E glass cloth, the effect of lowering the dielectric constant is not sufficient, which is not preferable.

The thermosetting resin component of the present invention is preferably blended in an amount of 100 to 900 parts by weight based on 100 parts by weight of the Br compound represented by the general formula (1). If it is less than 100 parts by weight, the Br compound of the general formula (1) is an addition type flame retardant, so that the thermosetting component is reduced and the heat resistance is lowered, which is not preferable. It is not preferable because the burning effect is diminished.

Examples of the thermosetting resin component of the present invention include:
A cyanate ester compound represented by the general formula (2) and / or a prepolymer thereof, a phenol compound represented by the general formula (3), an epoxy resin represented by the general formula (4),
A polyphenylene ether resin represented by the general formula (5),
There are adducts represented by the general formula (6) by addition of tetramethylcyclotetrasiloxane and a compound having two or more unsaturated groups in the molecule, triallyl isocyanurate, triallyl cyanurate, divinylbenzene, etc., These resin components may be used alone or in combination of two or more.

[Chemical 2]

The cyanate ester compound represented by the general formula (2) and / or its prepolymer used in the present invention means an organic compound having two or more cyanate ester groups in the molecule. In the present invention, the polyfunctional cyanate ester itself or a prepolymer derived therefrom can be used. These compounds, if necessary, by using a catalyst such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octylate, tin octylate, lead acetylacetonate, dibutyltin maleate, The cyanate ester group can be trimerized and the reaction can be appropriately adjusted to form a prepolymer. The cyanate ester group is
It is possible to form a sym-triazine ring in the molecule by trimerization and finally to heat-cure it. The cured product of the cyanate ester compound and / or the prepolymer thereof alone is excellent in heat resistance and has a low dielectric constant and dielectric properties, but the flame retardancy is still insufficient. It is possible to provide a resin which is excellent in heat resistance, flame retardancy, adhesiveness, chemical resistance and excellent in dielectric properties required for a resin for a high frequency substrate only after being mixed with a Br compound and cured by heating.

The cyanate ester compound used in the present invention is not particularly limited as long as it is represented by the general formula (2), but specific examples are 1,3-dicyanate benzene, 1, 4-dicyanate benzene, 1,3,5-
Tricyanate benzene, 1,8- or 2,6- or 2,7-dicyanate naphthalene, 4,4'-dicyanate biphenyl, bis (4-cyanatophenyl) methane, 2,2-bis (4 -Cyanatophenyl) propane, bis (3,5-dimethyl-4-cyanatophenyl) methane, 2,2-bis (3,5-dimethyl-4-cyanatophenyl) propane, bis (4-cyanatophenyl) ) Sulfone, tris (4-cyanatophenyl) phosphite, 1,1-bis (4-cyanatophenyl) ethane, 2,2-bis (4-cyanatophenyl) hexafluoropropane and the like.

The phenol compound used in the present invention is represented by the general formula (3), but since it has a phenolic hydroxyl group in the molecule, it can also function as a curing agent for an epoxy resin, and can also function as a cyanate ester compound. It also functions as a trimerization accelerator. Further, since the molecular skeleton has an aliphatic cyclized structure, it also has a function of lowering the values of the dielectric constant and the dielectric loss tangent, which is preferable.
Specific examples of the phenol compound used in the present invention include special phenol resin PP-700-300 manufactured by Nippon Oil Co., Ltd.,
There are PP-700-180, PP-1000-180, etc., but the invention is not limited to these. When combined with an epoxy group, a reaction accelerator such as imidazole can be used to accelerate the reaction.

Since the epoxy resin represented by the general formula (4) used in the present invention has a bulky alkyl substituent in the molecule as compared with the conventional bisphenol A type epoxy resin, the relative dielectric constant of the cured product is It is possible to reduce the value.

The polyphenylene ether resin represented by the general formula (5) used in the present invention has a small relative dielectric constant, and can be made thermosetting by addition of a radical catalyst or the like.

The cyclic siloxane / unsaturated compound adduct represented by the general formula (6) used in the present invention undergoes a hydrosilylation reaction in the presence of chloroplatinic acid, a radical initiator and the like, and is thermosetting. However, since it does not contain an acidic group in the molecule, it has a small relative dielectric constant and is a thermosetting resin component excellent in dielectric properties. Examples of the compound having two or more unsaturated groups in the molecule include dicyclopentadiene, divinylbenzene, triallyl isocyanurate, triallyl cyanurate, and the like.
It is not particularly limited to these.

The triallyl isocyanurate, triallyl cyanurate, divinylbenzene and the like used in the present invention are capable of radical crosslinking and hydrosilylation reaction and can be a thermosetting component. The dielectric properties of the product are also good.

The flame-retardant low dielectric constant thermosetting resin composition of the present invention is achieved by combining a specific flame retardant and a specific thermosetting resin component, but does not adversely affect the characteristics. Within the range, additives such as flame retardants and thermosetting resin components other than the above, various reaction catalysts, accelerators, fillers, colorants, coupling agents and the like may be added as appropriate.

The resin composition of the present invention is used in various forms, but a solvent is often used when coating and impregnating a substrate. It is necessary that the solvent used has 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, toluene, xylene, aromatic hydrocarbon solvents such as 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, methylse Solve solvent acetate, ethyl cellosolve acetate, butyl cellosolve acetate, ester solvent such as ethyl acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dialkyl glycol ether solvent 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 several of them can be used in combination.

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

[0020]

EXAMPLES The present invention will now be described in more detail by way of examples.

(Example 1) B manufactured by Yuka Shell Epoxy Co., Ltd.
r compound 5203 100 parts by weight, 2,2-bis (4-cyanatophenyl) propane 200 parts by weight, special phenol compound PP-700-180 manufactured by Nippon Oil Co., Ltd. 200 parts by weight, and toluene / methyl ethyl ketone 1: 1 Non-volatile concentration 50% by adding mixed solvent
The varnish solution was adjusted so that For this solution
When 10% nonylphenol solution of cobalt naphthenate was gradually added to adjust the gel time of the varnish on the heating plate at 170 ° C to 4 minutes ± 15 seconds, it was 3 minutes 58 seconds when 0.5 part by weight was added. .

Then, using this varnish, 100 parts of glass cloth (thickness 0.18 mm, E glass manufactured by Nitto Boseki Co., Ltd.) was impregnated with 100 parts of the varnish with a solid content, and dried in a drying oven at 150 ° C. for 4 minutes. A prepreg having a resin content of 50 wt% was prepared by drying. The obtained prepreg was tack-free and had excellent workability. 8 pieces of the above-mentioned dried prepregs are piled up and the thickness is 35
Overlaid with electrolytic copper foil of μm, pressure 40kgf / cm ² , temperature 175 ℃
It was heated and pressed for 90 minutes to obtain a laminated plate having a thickness of 1.6 mm.
After removing the surface copper foil of this laminate by etching, 121 ° C
Was treated under a pressure cooker condition of 2.0 atm for 20 hours, and the weight increase was measured. The same test piece was immersed in methylene chloride at room temperature for 10 minutes, and the appearance was checked to check the solvent resistance. The results are shown in Table 2.

The dielectric constant and dielectric loss tangent are measured according to JIS C.
It carried out according to 6481 and measured and calculated | required the electrostatic capacitance of frequency 1MHz. JIS C for solder heat resistance and peel strength
It was measured according to 6481, and the solder heat resistance was examined at 260 ° C. for 300 seconds to see if there was any abnormality in the appearance. The 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. The results are shown together in Table 2.

(Examples 2 to 6 and Comparative Examples 1 to 7) Laminated plates were produced in the same manner as in Example 1 except for the formulation shown in Table 1 and the results are shown in Table 2. .

[0025]

[Table 1] * 1: Yuka Shell Epoxy Co., Ltd.

[Chemical 3] * 2: Specialty petroleum compound manufactured by Nippon Oil Co., Ltd. * 3:

[Chemical 4] * 4: Contains 0.02 parts by weight of chloroplatinic acid

[Chemical 5] * 5: Poly (2,6-dimethylphenylene oxide) * 6: Epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd. * 7: Br epoxy resin manufactured by Sumitomo Chemical Co., Ltd. (Br content 40%) * 8: Sumitomo Durez Co., Ltd. phenol novolac * 9: Sumitomo Chemical Co., Ltd. bismaleimide resin * 10: Cured product with a dielectric constant of more than 3.2

[0026]

[Table 2]

[0027]

As is clear from the results of Tables 1 and 2, the resin composition of the present invention has a low dielectric constant, a low dielectric loss tangent, adhesion to metal, flame retardancy, heat resistance and chemical resistance. It is also an excellent thermosetting resin composition. Therefore, it is an optimal 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 laminate resin, which is an industrial advantage. Is large.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C08L 71/12 LQM 9167-4J 83/04 LRT 8319-4J (72) Inventor Sumiya Miyake Tokyo 1-2-2 Uchisaiwaicho, Chiyoda-ku Sumitomo Bakelite Co., Ltd.

Claims (7)

[Claims] 1. A Br compound 100 represented by the general formula (1).
A flame-retardant low dielectric constant thermosetting resin composition comprising 100 to 900 parts by weight of a thermosetting resin component having a relative dielectric constant of 3.2 or less when measured at 1 MHz. [Chemical 1] 2. A cyanate ester compound represented by the general formula (2) and / or a prepolymer thereof, a phenol compound represented by the general formula (3), and an epoxy resin represented by the general formula (4). A polyphenylene ether resin represented by the general formula (5), an adduct represented by the general formula (6) by addition of tetramethylcyclotetrasiloxane and a compound having two or more unsaturated groups in the molecule, triallyl isocyanate The flame-retardant low-dielectric-constant thermosetting resin composition according to claim 1, which is composed of one kind or a combination of two or more kinds selected from nurate, triallyl cyanurate and divinylbenzene. 3. The thermosetting resin component comprises a cyanate ester compound represented by the general formula (2) and / or a prepolymer thereof and a phenol compound represented by the general formula (3). Flame-retardant low dielectric constant thermosetting resin composition of. 4. The flame-retardant low-dielectric component according to claim 1, wherein the thermosetting resin component is composed mainly of an epoxy resin represented by the general formula (4) and a polyphenylene ether resin represented by the general formula (5). Rate thermosetting resin composition. 5. The flame-retardant low dielectric constant according to claim 1, wherein the thermosetting resin component comprises an epoxy resin represented by the general formula (4) and a phenol compound represented by the general formula (3). Thermosetting resin composition. 6. An adduct represented by the general formula (6), wherein the thermosetting resin component is the addition of tetramethylcyclotetrasiloxane and a compound having two or more unsaturated groups in the molecule.
The flame-retardant low dielectric constant thermosetting resin composition according to claim 1, which comprises 100 parts by weight and 0.002 to 0.2 parts by weight of a curing catalyst. 7. The thermosetting resin component comprises a cyanate ester compound represented by the general formula (2) and / or a prepolymer thereof, a polyphenylene ether resin represented by the general formula (5), and divinylbenzene. Flame-retardant low dielectric constant thermosetting resin composition of. [Chemical 2]