JP3330416B2 - Flame retardant 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]

DISCLOSURE OF THE INVENTION The present invention has been studied diligently to obtain a thermosetting resin having flame retardancy, low dielectric constant, low dielectric loss tangent, high heat resistance, high adhesiveness and excellent workability. It is the result of repeating.

[0005]

According to the present invention, there is provided a compound represented by the general formula (1):
100 parts by weight of a Br compound represented by the following formula, and having a relative dielectric constant of 3.2 or less when measured at 1 MHz.
A flame-retardant low dielectric constant thermosetting resin composition comprising 0 parts by weight.

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[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 tends to decrease the dielectric properties with an increase in the amount of the flame retardant, but the compound represented by the general formula (1) used in the present invention has a characteristic that its adverse effect is extremely small. Which is a very suitable compound for achieving both dielectric properties and flame retardancy. Further, by combining this Br compound and a thermosetting resin component having a low dielectric constant, the flame-retardant low-dielectric constant thermosetting resin composition of the present invention can be obtained.

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

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 of the general formula (1). If the amount is less than 100 parts by weight, the Br compound of the general formula (1) is an addition-type flame retardant, so that the amount of the thermosetting component is reduced and the heat resistance is lowered. It is not preferable because the effect of burning is weakened.

[0009] in minutes thermosetting resin forming the present invention, a cyanate ester compound represented by the general formula (2) and / or a prepolymer thereof, phenol compound represented by the general formula (3), the general formula (4 ), A polyphenylene ether resin represented by the general formula (5), and a compound represented by the general formula (6) by addition of tetramethylcyclotetrasiloxane and a compound having two or more unsaturated groups in the molecule. adduct, triallyl isocyanurate, triallyl cyanurate, there is divinylbenzene, these resin components are used in combination of one or two or more, ingredients
Physically, a cyanate ester represented by the general formula (2)
A compound and / or a prepolymer thereof and a compound represented by the general formula (3)
Component mainly composed of phenolic compounds, thermosetting resin
An epoxy resin whose component is represented by the general formula (4) and a general formula
Mainly polyphenylene ether resin shown in (5)
Component, an epoxy resin represented by the general formula (4) and a general formula
A component mainly composed of a phenolic compound represented by (3),
Tramethylcyclotetrasiloxane and two or more in the molecule
Formula (6) by addition of a compound having an unsaturated group
100 parts by weight of the adduct represented by and the curing catalyst 0.002-0.2 weight
A cyanate represented by the general formula (2):
Ester compound and / or its prepolymer and general formula
A polyphenylene ether resin represented by (5),
Ru component der comprising a vinyl benzene.

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The cyanate ester compound represented by the general formula (2) 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, by using a catalyst such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octylate, tin octylate, lead acetylacetonate, dibutyltin maleate, etc. The cyanate ester group can be trimerized, and the reaction can be appropriately adjusted to form a prepolymer. The cyanate ester group is
By trimerizing, it is possible to form a sym-triazine ring in the molecule, and finally to heat and cure. The cured product of the cyanate ester compound and / or its prepolymer alone has excellent heat resistance and provides low dielectric constant and dielectric properties, but has insufficient flame retardancy, and has the following formula (1). Only by blending with a Br compound and heating and curing, it is possible to provide a resin having excellent heat resistance, flame retardancy, adhesiveness, and chemical resistance, and also having excellent dielectric properties required for a resin for a high-frequency substrate.

The cyanate ester compound used in the present invention is not particularly limited as long as it is represented by the general formula (2). Specific examples include 1,3-dicyanatobenzene and 1,3-dicyanatobenzene. 4-dicyanatobenzene, 1,3,5-
Tricyanatobenzene, 1,8- or 2,6- or 2,7-dicyanatonaphthalene, 4,4'-dicyanatobiphenyl, 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). Since it has a phenolic hydroxyl group in the molecule, it can function as a curing agent for an epoxy resin. It also functions as a trimerization promoter. Further, since the molecular skeleton has an aliphatic cyclized structure, it has a function of lowering the dielectric constant and the dielectric loss tangent, which is preferable.
Specific examples of the phenol compound used in the present invention include a special phenol resin PP-700-300, manufactured by Nippon Oil Co., Ltd.
There are PP-700-180, PP-1000-180, etc., but it is not particularly limited to these. When combined with an epoxy group, a reaction accelerator such as imidazole can be used to accelerate the reaction.

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, and therefore has a low dielectric constant of the cured product. The value can be reduced.

The polyphenylene ether resin represented by the general formula (5) used in the present invention itself has a small relative dielectric constant, and can be made thermosetting by adding 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, etc. 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 having excellent 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 can be radically cross-linked and can also undergo a 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 a combination of a specific flame retardant and a specific thermosetting resin component, but does not adversely affect the properties. As long as it is within the range, additives such as a flame retardant, a thermosetting resin component, various reaction catalysts, an accelerator, a filler, a coloring agent, and a coupling agent other than those described above may be appropriately 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 is a woven glass cloth, a non-woven 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.

[0020]

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

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

Thereafter, 100 parts of a glass cloth (0.18 mm thick, E-glass manufactured by Nitto Boseki Co., Ltd.) is impregnated with 100 parts of the varnish with a solid content using the varnish, and the varnish is placed in a drying oven at 150 ° C. for 4 minutes. It was dried to prepare a prepreg having a resin content of 50 wt%. The obtained prepreg was tack-free and excellent in workability. Lay 8 dried prepregs above and 35
μm electrodeposited copper foil, pressure 40kgf / cm ² , temperature 175 ℃
Heat and pressure molding was performed for 90 minutes to obtain a laminate having a thickness of 1.6 mm.
After the surface copper foil of this laminate is removed by etching,
For 20 hours under a pressure cooker condition at a pressure of 2.0 atm, 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 based on JIS C
The measurement was performed in accordance with 6481, and the capacitance at a frequency of 1 MHz was measured. JIS C 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. Table 2 shows the results together.

(Examples 2 to 6 and Comparative Examples 1 to 7) Laminates were manufactured in the same manner as in Example 1 except that the composition was as shown in Table 1 and the results are shown in Table 2. .

[0025]

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

Embedded image * 2: Special phenolic compound manufactured by Nippon Oil Co., Ltd. * 3:

Embedded image * 4: Including 0.02 parts by weight of chloroplatinic acid

Embedded image * 5: Poly (2,6-dimethylphenylene oxide) * 6: Epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd. * 7: Br-modified epoxy resin manufactured by Sumitomo Chemical Co., Ltd. (Br content 40%) * 8: Phenol novolak manufactured by Sumitomo Durez Co., Ltd. * 9: Bismaleimide resin manufactured by Sumitomo Chemical Co., Ltd. * 10: A cured product whose relative dielectric constant exceeds 3.2

[0026]

[Table 2]

[0027]

As is clear from the results shown in 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 a thermosetting resin composition which is also excellent. 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.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Sumiya Miyake 1-2-2 Uchisaiwaicho, Chiyoda-ku, Tokyo Sumitomo Bakelite Co., Ltd. Examiner Tamotsu Fujimoto (56) References JP-A-3-275760 (JP, A JP-A-3-50259 (JP, A) JP-A-59-53524 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3 / 00-13/08

Claims (5)

(57) [Claims] 1. A Br compound 100 represented by the general formula (1)
Parts by weight, having a relative dielectric constant of 3.2 or less when measured at 1 MHz, and a cyanate ester compound represented by the general formula (2):
And / or a prepolymer thereof, represented by the general formula (3)
Phenol compound, epoxy represented by general formula (4)
Resin, polyphenylene ether represented by general formula (5)
Resin, tetramethylcyclotetrasiloxane and intramolecular
General by addition with compounds having two or more unsaturated groups
Adduct of formula (6), triallyl isocyanurate
G, triallyl cyanurate or divinylbenzene
Heat consisting of 100 to 900 parts by weight of thermosetting resin component selected from
A curable resin composition, wherein the thermosetting resin component has a general formula
A cyanate ester compound represented by (2) and / or
The prepolymer and a phenol represented by the general formula (3)
A flame-retardant low dielectric constant thermosetting resin composition comprising a component mainly composed of a compound. Embedded image Embedded image 2. The flame-retardant low dielectric substance according to claim 1, wherein the thermosetting resin component mainly comprises an epoxy resin represented by the general formula (4) and a polyphenylene ether resin represented by the general formula (5). Rate thermosetting resin composition. 3. The flame-retardant low dielectric constant according to claim 1, wherein the thermosetting resin component comprises a component mainly composed of an epoxy resin represented by the general formula (4) and a phenol compound represented by the general formula (3). Thermosetting resin composition. 4. An adduct represented by the general formula (6) wherein the thermosetting resin component is obtained by adding tetramethylcyclotetrasiloxane to a compound having two or more unsaturated groups in a molecule.
The flame-retardant low dielectric constant thermosetting resin composition according to claim 1, comprising 100 parts by weight and 0.002 to 0.2 parts by weight of a curing catalyst. 5. 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.