JP2000239496A - Cyanate/epoxy resin composition, and prepreg, metal-clad laminate and printed wiring board made by using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cyanate/epoxy resin composition having high glass transition temperature, excellent dielectric properties and low percentage of water absorption without deteriorating the characteristics such as heat resistance and adhesiveness. SOLUTION: The cyanate/epoxy resin composition contains (A) a cyanate compound containing at least tow cyanato groups in the molecule, (B) an epoxy resin, and (C) a cure accelerator as the principal constituents, wherein the epoxy resin comprises one derived from a dicyclopentadiene-phenol polyaddition product containing a dicyclopentadiene skeleton represented by the formula wherein n is 0 or a positive integer and wherein the cure accelerator used comprises a mixture of a compound having such a catalytic function as to accelerate the curing reaction of the cyanate compound (A) and a compound having such a catalytic function as to accelerate the curing reaction of the epoxy resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a cyanate / epoxy resin composition containing a cyanate compound and an epoxy resin, and a prepreg, a metal foil-clad laminate and a printed wiring board using the same.

[0002]

2. Description of the Related Art In recent years, advanced communication and information technology in which a computer and a communication device are integrated has been developed. Computers are downsized to become smaller systems, which also require the same processing capacity as conventional large machines. In addition, miniaturization, weight reduction, and high performance of information terminal devices typified by mobile phones, personal computers, and the like, which are rapidly spreading, are being promoted. Printed wiring boards mounted on these devices are becoming denser and thinner, and are required to have high heat resistance and high insulation reliability. Further, in order to cope with an increase in signal speed and an increase in frequency, a material having a low relative dielectric constant and a low dielectric loss tangent is required. In order to respond to such a demand, a method of curing a polyfunctional epoxy resin with dicyandiamide or a method of curing with a polyfunctional phenol resin has been performed as a method of improving heat resistance of a printed wiring board using an epoxy resin composition. I have.

Further, the following proposals have been made for the purpose of improving the dielectric properties of an epoxy resin printed wiring board having excellent heat resistance. For example, epoxy resin is disclosed in
No. 0-135425, poly-4-methyl-1-pentene, phenol-added butadiene polymer described in JP-A-61-126162, disclosed in JP-A-62-187736. Reaction with a polybutadiene modified with a terminal carboxy group or a propargyl etherified aromatic hydrocarbon disclosed in JP-A-4-13717. Also, Japanese Patent Application Laid-Open No. 57-8
No. 3090, a method of mixing hollow particles in a resin layer, a method of blending a fluororesin powder described in JP-A-2-203594,
No. 84040 discloses a method using an aromatic polyamide fiber as a base material. As shown in Japanese Patent Application Laid-Open No. 4-24986, a glass cloth base fluororesin prepreg and a glass cloth base epoxy resin prepreg are laminated. And the like.

On the other hand, resin materials such as cyanate ester resin and BT resin (bismaleimide-triazine resin) have been proposed as resin materials having both high heat resistance and low dielectric properties other than epoxy resin-based materials. However, these have the drawback that they have high water absorption and are inferior in adhesiveness, heat resistance when absorbing moisture, and the like.

Therefore, cyanate ester resins and BT
(Bismaleimide-triazine) In order to improve the above-mentioned disadvantages of the resin, glycidyl etherified product of phenol novolak disclosed in JP-A-63-54419 and bisphenol A disclosed in JP-A-3-84040 are disclosed. There is a method in which an epoxy resin such as a glycidyl ether compound is used in combination with an epoxy resin such as a glycidyl ether compound of a brominated phenol novolak disclosed in JP-A-2-286723.

In the method of curing a polyfunctional epoxy resin with dicyandiamide, the dicyandiamide cured system has a disadvantage of increasing the hygroscopicity, and it is difficult to satisfy high insulation reliability for semiconductor package applications. In particular, the occurrence of metal migration (electrolytic corrosion) in which a metal constituting wiring, a circuit pattern, or an electrode moves on or in an insulating material due to the action of a potential difference in a high-humidity environment on or in the insulating material. It has become a very big problem. Further, in the method of curing with a polyfunctional phenol resin, the cured polyfunctional phenol resin has a rigid resin cured material, and minute cracks are easily generated when drilling a through hole, and metal migration occurs from the minute cracks. Therefore, high insulation reliability cannot be satisfied.

Further, Japanese Patent Application Laid-Open No. 60-135425,
JP-A-61-126162 and JP-A-62-18
No. 7736, poly-4-methyl-1-pentene, phenol-added butadiene polymer,
The method of reacting a hydrocarbon polymer such as polybutadiene modified with a terminal carboxy group with an epoxy resin has a problem that the inherent heat resistance of the epoxy resin is impaired although the dielectric constant is lowered. The method of reacting with a propargyl etherified aromatic hydrocarbon disclosed in JP-A-4-13717 has a problem that the heat resistance is high but the cost is extremely high because a special resin is used.

Further, a method of mixing hollow particles in a resin layer, a method of blending a fluororesin powder, a method of blending a fluororesin powder, and a method disclosed in JP-A-57-83090 and JP-A-2-203594. No. 84040 and Japanese Patent Laid-Open No.
In the method using an aromatic polyamide fiber on a substrate as described in Japanese Patent No. 24986 or a method using a glass cloth substrate with a fluororesin prepreg laminated thereon, the dielectric constant as a laminate is low, but the conventional glass cloth There was a problem that the mechanical properties were lower than that of the base epoxy resin laminate.

Further, in the method disclosed in Japanese Patent Application Laid-Open No. 3-84040, in which an epoxy resin is mixed with a cyanate ester resin, the adhesiveness is improved, but the water absorption is reduced and the heat resistance during moisture absorption is improved. Has no significant effect. In the method using an epoxy resin as disclosed in JP-A-63-54419, a decrease in Tg can be suppressed to some extent, and the heat resistance at the time of moisture absorption and the adhesion to metal can be improved, but the water absorption rate is low. However, there is a drawback that it increases, and no significant effect is seen in improving workability.
Further, in the glycidyl etherified product of brominated phenol novolak disclosed in JP-A-2-286723, workability, heat resistance at the time of moisture absorption and flame resistance can be added, but the problem that water absorption is deteriorated remains. ing.

[0010]

SUMMARY OF THE INVENTION The present invention provides a cyanate having a high glass transition temperature, excellent dielectric properties and a low water absorption without deteriorating properties such as heat resistance and adhesiveness.
An object of the present invention is to provide an epoxy resin composition and a prepreg, a metal foil-clad laminate and a printed wiring board using the same.

[0011]

The present invention relates to the following. (1) (A) a cyanate compound containing two or more cyanato groups in one molecule, (B) an epoxy resin, (C)
In a resin composition containing a curing accelerator as a main component, the epoxy resin is an epoxy resin derived from a dicyclopentadiene-phenol polyadduct containing a dicyclopentadiene skeleton represented by the formula (1), and curing is accelerated. As an agent, a compound having a catalytic function of accelerating a curing reaction of a cyanate compound containing two or more cyanato groups in one molecule and a compound having a catalytic function of accelerating a curing reaction of an epoxy resin are used in combination. Cyanate / epoxy resin composition.

Embedded image (Where n represents 0 or a positive integer) (2) A compound having a catalytic function of accelerating the curing reaction of a cyanate compound containing two or more cyanato groups in one molecule is an organic metal salt or The cyanate / epoxy resin composition according to item (1), wherein the compound that is an organometallic complex and has a catalytic function of accelerating the curing reaction of the epoxy resin is an imidazole compound. (3) The cyanate / epoxy resin composition according to item (2), wherein the organic metal salt or the organic metal complex is an organic metal salt or an organic metal complex of iron, copper, zinc, cobalt, nickel, manganese, or tin. (4) (A) 50 to 250 parts by weight of an epoxy resin and (C) 0.1 parts by weight of a curing accelerator, based on 100 parts by weight of a cyanate compound containing two or more cyanato groups in one molecule. The cyanate / epoxy resin composition according to any one of items (1) to (3), wherein the composition contains 1 to 5 parts by weight. (5) Further, items (1) to (D) containing an antioxidant (D)
The cyanate / epoxy resin composition according to any one of (4). (6) The item (5) according to item (5), wherein (A) 0.1 to 20 parts by weight of (D) an antioxidant is contained with respect to 100 parts by weight of a cyanate compound containing two or more cyanato groups in one molecule. Cyanate / epoxy resin composition. (7) A prepreg obtained by impregnating a substrate with the cyanate / epoxy resin composition according to any one of (1) to (6) and drying the substrate. (8) A metal foil-clad laminate obtained by laminating a metal foil on one or both surfaces of the prepreg or the laminate thereof according to item (7), and subjecting the metal foil to heat and pressure molding. (9) A printed wiring board obtained by performing circuit processing on the metal foil of the metal foil-clad laminate according to item (8).

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The (A) cyanate compound containing two or more cyanato groups in one molecule used in the cyanate / epoxy resin composition of the present invention is a compound represented by the following formula (2): is there. 2,2-bis (4-cyanatephenyl) propane, bis (3,5-dimethyl-4-cyanatephenyl) methane, 2,2-bis (4-cyanatephenyl) 1,1,1,3,3,3 -Hexafluoropropane, α, α'-bis (4-cyanatephenyl)
-M-diisopropylbenzene and the like.

[0013]

Embedded image (Wherein, R ₁ is an alkylene group having 1 to 3 carbon atoms which may be substituted with halogen;

Embedded image (Where R ₅ represents an alkylene group of an alkylene group having 11 to 13 carbon atoms, and two R _{5 's} may be the same or different) or

Embedded image R ₂ and R ₃ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different, and two R ₃ may be the same or different, R ₄ may be the same or different. The preferred specific examples of R1 are as follows:

Embedded image There is.

In the present invention, (A) 2 is used in one molecule.
Monomers of cyanate compounds containing two or more cyanato groups have high crystallinity, and when these monomers are varnished with a solvent, they may recrystallize in the varnish depending on the solid content concentration. Therefore, it is preferable that the above-mentioned cyanate compound monomer is prepolymerized before use.

The prepolymer comprises a monomer of a cyanate compound containing two or more cyanato groups in one molecule,
If necessary, the reaction is carried out in the presence of an organometallic salt or an organometallic complex having a catalytic function to accelerate the reaction of the cyanate compound, thereby increasing the amount of the cyanate group. In particular, a cyanate group is cyclized (triazine cyclization). It can be obtained by: The conversion of the monomer of the cyanate compound is 10 to 7
The reaction is preferably performed so as to be 0 mol%, and particularly preferably the reaction is performed at 30 to 60 mol%. If the conversion is too small, the cyanate compound may be recrystallized when varnished due to strong crystallinity. On the other hand, if the conversion is too high, the viscosity of the varnish becomes high, impregnating the glass substrate or the like may be impaired, and the smoothness of the prepreg surface may be lost. The storage stability (pot life) of the varnish tends to be lost due to the possibility that the varnish may become so short that it becomes a problem in the work.

Further, in the present invention, (A) a prepolymer obtained by prepolymerizing a monomer of a cyanate compound containing two or more cyanato groups in one molecule,
In many cases, the composition contains a monomer, but preferably has a number average molecular weight of 250 to 1,000, and particularly preferably has a number average molecular weight of 300 to 800. The number average molecular weight is measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve. If the molecular weight is too small, it may recrystallize when varnished for the strong crystallinity of the cyanate compound as described above, and if the molecular weight is too large, the viscosity when varnished becomes high and the glass substrate etc. There is a tendency that the impregnating property is reduced and the smoothness of the prepreg surface is impaired, or the gelling time becomes so short as to be a problem in the coating operation, and the storage stability (pot life) of the varnish tends to be lost. Such prepolymers are known as Ar
Ocy B-30 and Arocy M-30 (both are trade names manufactured by Asahi Ciba Co., Ltd.) can be used.

The epoxy resin (B) used in the present invention comprises, as essential components, an epoxy resin derived from a dicyclopentadiene-phenol polyadduct having a dicyclopentadiene skeleton represented by the formula (1). Another one
An epoxy resin having two or more epoxy groups in the molecule may be used in combination. The epoxy resin (B) used in the present invention comprises, as an essential component, an epoxy resin derived from a dicyclopentadiene-phenol polyaddition product having a dicyclopentadiene skeleton represented by the formula (1), and another epoxy resin. An epoxy compound having two or more epoxy groups in the molecule may be used in combination. The epoxy resin of the formula (1) is (,
B) It is preferably 15 to 100% by weight, preferably 30 to 100% by weight, based on the total amount of the epoxy resin. 1
If the content is less than 5% by weight, the Tg (glass transition temperature change) of the cured product tends to decrease and the water absorption tends to increase. When a halogenated (especially brominated) epoxy resin is used for flame retardation, at least the amount excluding the used amount is expressed by the formula (1).
Should be the upper limit of the amount of epoxy resin used. The halogen content is preferably 10 to 25% by weight based on the solid content of the resin. The dicyclopentadiene-phenol polyadduct containing a dicyclopentadiene skeleton represented by the formula (1) is preferably one in which n in the formula (1) is 5 or less.

Examples of the epoxy resin used in combination include bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol type epoxy resin, biphenyl type epoxy resin, phenol salicylaldehyde novolak type epoxy resin and the like. Further, examples of the halogenated epoxy resin for securing the flame resistance as a printed wiring board include brominated epoxy resins such as a brominated bisphenol A type epoxy resin and a brominated phenol novolak type epoxy resin. From the viewpoint of dielectric properties, brominated bisphenol A type epoxy resin is preferred.

The amount of the epoxy resin (B) used in the cyanate / epoxy resin composition of the present invention is (A)
(B) epoxy resin is added to 5 parts by weight of 100 parts by weight of a cyanate compound containing two or more cyanato groups in one molecule.
It is preferably from 0 to 250 parts by weight. If the amount is less than 50 parts by weight, the heat resistance at the time of moisture absorption tends to deteriorate. If the amount exceeds 250 parts by weight, the dielectric properties deteriorate and the glass transition temperature (T
g) tends to decrease, which is not preferred. More preferably, it is 100 to 230 parts by weight.

The (C) curing accelerator used in the present invention comprises (A) a compound having a catalytic function of accelerating the curing reaction of a cyanate compound containing two or more cyanato groups in one molecule, and (B) an epoxy compound. A compound having a catalytic function of accelerating the curing reaction of the resin is used in combination.

(A) As a compound having a catalytic function of accelerating the curing reaction of a cyanate compound containing two or more cyanato groups in one molecule, there is an organic metal salt or an organic metal complex. Examples of the metal of the organic metal salt or the organic metal complex include iron, copper, zinc, cobalt, nickel, manganese, and tin. Examples of the organic metal salts include iron naphthenate, copper naphthenate, zinc naphthenate, cobalt naphthenate, nickel naphthenate, manganese naphthenate, tin naphthenate octyl zinc, tin octylate, and zinc ethyl ethylhexanoate. Examples of the organometallic complex include dibutyltin maleate and lead acetylacetonate. It is preferred that these are blended in an amount of 0.05 to 3 parts by weight based on 100 parts by weight of the cyanate compound (A) having two or more cyanato groups in one molecule.
If the amount is less than 0.05 parts by weight, the catalyst function is inferior and the curing time is prolonged. If it exceeds 3 parts by weight, the storage stability of varnish and prepreg tends to be poor. 0.1 to 1.0 part by weight is more desirable.

Examples of the compound (B) having a catalytic function of accelerating the curing reaction of the epoxy resin include imidazole compounds, organic phosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts. However, among these, imidazole compounds are most preferred.

Examples of the imidazole compounds include imidazole compounds such as imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole,
-Benzyl-2-methylimidazole, 2-heptadecylimidazole, 4,5-diphenylimidazole,
-Methylimidazoline, 2-phenylimidazoline, 2
-Undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethylimidazoline, 2-isopropylimidazoline, 2,4-dimethylimidazoline, -Phenyl-4-methylimidazoline and the like, and examples of the masking agent include acrylonitrile, phenylene diisocyanate, toluidine isocyanate, naphthalene diisocyanate, methylene bisphenyl isocyanate, melamine acrylate and the like.

Examples of the organic phosphorus compound include triphenylphosphine and the like; piperidine and the like; tertiary amines such as dimethylbenzylamine and tris (dimethylaminomethyl) phenol; quaternary ammonium salts such as tetrabutylammonium bromide; And tetrabutylammonium chloride.

The amount of the compound having a catalytic function for accelerating the curing reaction of the epoxy resin is preferably 0.05 to 3 parts by weight based on 100 parts by weight of the epoxy resin. If the amount is less than 0.05 parts by weight, the catalyst function is inferior and the curing time is prolonged. On the other hand, when the amount exceeds 3 parts by weight, the storage stability of the varnish or prepreg becomes poor.

In the present invention, the total amount of the curing accelerator is
(A) The content is preferably 0.1 to 5 parts by weight based on 100 parts by weight of a cyanate compound containing two or more cyanato groups in one molecule. If the amount is less than 0.1 part by weight, the catalyst function is inferior and the curing time tends to be long. If it exceeds 5 parts by weight, the storage stability of varnish and prepreg tends to be poor.

The (D) antioxidant used in the cyanate / epoxy resin composition of the present invention includes a phenolic antioxidant, a sulfur organic compound antioxidant and the like.
Specific examples of phenolic antioxidants include pyrogallol, butylated hydroxyanisole, 2,6-di-t-
Monophenols such as butyl-4-methylphenol and 2,2′-methylene-bis- (4-methyl-6-t-
Bisphenols such as butylphenol) and 4,4'-thiobis- (3-methyl-6-t-butylphenol); and 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-). Butyl-4-hydroxybenzyl)
Benzene, tetrakis- [methylene-3- (3'-5 '
-Di-t-butyl-4'-hydroxyphenyl) propionate] methane. Among the phenolic antioxidants, bisphenol-based antioxidants are particularly preferred in terms of effect. Specific examples of the sulfur organic compound-based antioxidant include diuralylthiodipropionate, distearylthiodipropionate, and the like. Some of these antioxidants may be used in combination. The (D) antioxidant of the present invention comprises (A) 2 molecules per molecule.
Cyanate compounds containing 10 or more cyanato groups
0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, is added to 0 parts by weight.
If the amount is less than 0.1 part by weight, no improvement in insulation properties is observed,
Conversely, if the amount exceeds the weight parts, the insulating properties tend to decrease.

The cyanate / epoxy resin composition of the present invention may optionally contain a filler and other additives. As the filler, usually, an inorganic filler is suitably used, and specifically, fused silica, glass, alumina, zircon, calcium silicate, calcium carbonate, silicon nitride, boron nitride, beryllia, zirconia, potassium titanate, and silicic acid Aluminum, magnesium silicate and the like are used as powder or spherical beads. Also, whiskers, single crystal fibers, glass fibers, inorganic and organic hollow fillers and the like can be blended. These compounding amounts are 5 to 100 parts by weight of the resin solid content.
It is preferable to mix it in an amount of up to 30 parts by weight. If the amount is less than 5 parts by weight, the effect of compounding the filler cannot be obtained. If the amount exceeds 30 parts by weight, the filler tends to settle or coagulate.

The cyanate / epoxy resin composition of the present invention is cured by heating to produce prepregs, laminates, metal foil-clad laminates and printed wiring boards having excellent dielectric properties and heat resistance and low water absorption. To be served. For this purpose, it is preferable to dissolve the cyanate / epoxy resin composition of the present invention in a solvent to once prepare a varnish. The solvent is not particularly limited, but ketones, aromatic hydrocarbons, esters, amides, alcohols and the like are used. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like are used as ketone solvents, toluene and xylene are used as aromatic hydrocarbon solvents, and methoxyethyl acetate, ethoxyethyl acetate and butoxy are used as ester solvents. Ethyl acetate, ethyl acetate and the like, amide solvents such as N-methylpyrrolidone, formamide, N-methylformamide, N, N-dimethylacetamide and the like; alcoholic solvents such as methanol, ethanol, ethylene glycol and ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, diethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol, Glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, and the like. These solvents may be used alone or in combination of two or more.

As the base material used for the prepreg, 3
A glass cloth of 0 μm to 200 μm is preferably used. The prepreg is produced by impregnating the varnish with a glass cloth and drying the glass cloth at a temperature of 140 ° C. to 200 ° C. for 3 to 15 minutes to obtain a B stage (semi-cured state). The impregnation amount at this time, with respect to the total amount of the varnish solids and the substrate,
It is preferable that the varnish solid content is 35 to 60% by weight. The prepreg can be made into a metal-foil-clad laminate by laminating one or an arbitrary number of layers as appropriate, laminating a metal foil on one or both sides thereof, and forming the laminate under heat and pressure. The condition at this time is that the heating temperature is 15
The conditions are preferably 0 to 230 ° C. and a pressure of 2 to 5 MPa, and it is preferable to expose to these conditions for 0.5 to 2.0 hours. Copper foil, aluminum foil and the like are used as the metal foil. The thickness of the metal foil depends on the application, but 10 to 100μ
m are preferably used.

The printed wiring board can be obtained by subjecting the metal foil of the metal foil-clad laminate to circuit processing. For circuit processing, for example, after forming a resist pattern on the metal foil surface, unnecessary portions of the foil are removed by etching, the resist pattern is peeled off, necessary through holes are formed by a drill, and a resist pattern is formed again, and a through hole is formed. The plating can be carried out by applying plating for electrical conduction and finally removing the resist pattern. On the surface of the printed wiring board thus obtained, the above-mentioned metal foil-clad laminate is further laminated under the same conditions as described above, and further, circuit processing is performed in the same manner as above to obtain a multilayer printed wiring board. be able to. In this case, it is not necessary to form a through hole, and a via hole may be formed, or both may be formed. Such multilayering is performed for a required number of sheets.

[0032]

In a general curing reaction of an epoxy resin, a highly polar hydroxyl group is generated along with the ring opening of the epoxy group, and therefore, there is a limit to lowering the dielectric constant. In addition, when a special curing agent represented by a hydrocarbon polymer such as phenol-added polybutadiene is used, the inherent heat resistance of the epoxy resin is impaired, and the glass transition is lower than when cured with a polyfunctional phenol resin or the like. There are problems such as low temperature and high cost. On the other hand, a cured product of a cyanate ester resin having a low-polarity, rigid and symmetric triazine skeleton has a low dielectric constant, a low dielectric loss tangent, and a high glass transition temperature, but has problems such as adhesiveness and heat resistance when absorbing moisture. There is. In order to solve this problem, a resin composition in which a conventional epoxy resin based on bisphenol A or brominated bisphenol A is used in combination with a cyanate ester resin causes problems such as an increase in water absorption and adhesion to metals. The cyanate of the present invention
The epoxy resin composition has a higher glass transition temperature, dielectric properties, heat resistance, and low water absorption as compared with the conventional epoxy resin-based resin composition for printed wiring boards or the resin composition using the above-described cyanate ester resin and epoxy resin in combination. Excellent in nature,
Although it is possible to obtain a cyanate / epoxy resin composition exhibiting a lower water absorption and a laminate and a printed wiring board using the same, in the present invention, in the combination of the cyanate compound and the specific epoxy resin in the present invention, ,
Furthermore, by using each curing accelerator together,
These effects can be obtained. Furthermore, by using an antioxidant, the corrosion resistance can be improved without impairing the above-mentioned properties.

[0033]

Hereinafter, the present invention will be described with reference to specific examples.
The present invention is not limited to these.

Example 1 (A) As a cyanate compound containing two or more cyanato groups in one molecule, a prepolymer of 2,2-bis (4-cyanatephenyl) propane (ArocyB-30,
Asahi Ciba product name, monomer reaction rate: about 46%,
Number average molecular weight: 560, cyanate equivalent: 200),
(B) Dicyclopentadiene type epoxy resin (HP7200H, trade name of Dainippon Ink and Chemicals, epoxy equivalent 287) and brominated bisphenol A type epoxy resin (ESB400T, trade name of Sumitomo Chemical Co., Ltd.) Epoxy equivalent 401) was dissolved in methyl ethyl ketone at the compounding amounts shown in Table 1, and (C) cobalt naphthenate and 2-methylimidazole (2MZ) were compounded as curing accelerators according to Table 1 to obtain a cyanate. An epoxy resin composition varnish was prepared.

Example 2 In Example 1, (A) 2,2-bis (4) of a cyanate compound containing two or more cyanato groups in one molecule was used.
-Cyanate phenyl) propane was replaced by bis (3,5-dimethyl-4-cyanatephenyl) methane prepolymer (Arocy M-30, trade name of Asahi Ciba Co., Ltd., monomer conversion: about 46%, number average molecular weight:
490, cyanate equivalent: 219) and dissolved in methyl ethyl ketone at the compounding amounts shown in Table 1. In Example 1, cobalt naphthenate was replaced by zinc naphthenate, and 2-methylimidazole was replaced by 2-ethyl-4-methylimidazole. A cyanate / epoxy resin composition varnish was prepared in the same manner as in Example 1 except that the composition was as shown in Table 1.

Example 3 In Example 1, (C) the curing accelerator, cobalt naphthenate, was replaced with manganese naphthenate, and 2-methylimidazole (2MZ) was replaced with 2-undecylimidazole (C11Z,
A cyanate / epoxy resin composition varnish was prepared in the same manner as in Example 1 except that the composition shown in Table 1 was used instead of Shikoku Chemicals Co., Ltd.).

Example 4 In Example 1, (C) Cobalt naphthenate as a curing accelerator was replaced with zinc naphthenate and 2-methylimidazole (2
A cyanate / epoxy resin composition varnish was prepared in the same manner as in Example 1 except that MZ) was changed to 2-undecylimidazole (C11Z, trade name, manufactured by Shikoku Chemicals Co., Ltd.) and the composition shown in Table 1.

Comparative Example 1 In Example 1, the dicyclopentadiene type epoxy resin was replaced with a bisphenol A type epoxy resin (DER331L,
Dow Chemical Japan Co., Ltd. product name, epoxy equivalent 18
A cyanate / epoxy resin composition varnish was prepared in the same manner as in Example 1 except that 5) was adopted.

Comparative Example 2 In Example 1, the only epoxy resin was bisphenol A type epoxy resin (DER331L, trade name of Dow Chemical Japan Co., Ltd., epoxy equivalent: 185). Example 1
A varnish of a cyanate / epoxy resin composition was prepared in the same manner as in the above.

Comparative Example 3 A varnish of a cyanate resin composition was prepared as shown in Table 1 except that no epoxy resin was blended in Example 1.

Comparative Example 4 A brominated bisphenol A type epoxy resin (ESB400T, trade name of Sumitomo Chemical Co., Ltd., epoxy equivalent 401) as an epoxy resin, and a phenol novolak resin (HP850N, trade name of Hitachi Chemical Co., Ltd.) as a curing agent , Hydroxyl equivalent 106) at an equivalent ratio of 1: 1 and dissolved in methyl ethyl ketone to prepare 2-methylimidazole as shown in Table 1 to prepare an epoxy resin composition varnish having a nonvolatile content of 70% by weight.

Comparative Example 5 A varnish of a cyanate / epoxy resin composition was prepared in the same manner as in Example 4 except that 2-undecylimidazole as a curing accelerator was not used.

The varnishes of Examples 1 to 4 and Comparative Examples 1 to 5 were impregnated into a 0.2 mm-thick glass cloth (basis weight: 210 g / m ² ) and dried at 160 ° C. for 5 minutes to obtain a prepreg. Four prepregs and 18 μm thick copper foil are laminated on top and bottom,
Press molding was performed for 1 hour at 70 ° C. and 2.45 MPa to produce a copper-clad laminate. Next, after forming an etching resist, a circuit was formed by etching to obtain a printed wiring board.
The steps from the formation of the etching resist to the etching were performed in a usual manner. The glass transition temperature (T
g), dielectric constant, solder heat resistance, water absorption, and flame resistance were evaluated.

The evaluation was performed as follows. Glass transition temperature (Tg): Measured by thermomechanical analysis (TMA method). Dielectric properties: Evaluated with a Neumann broadband dielectric property measuring device (gap change method). Solder heat resistance: A test piece cut into 50 mm x 50 mm is 121 ° C, 0.22MP with a pressure cooker.
After absorbing moisture for 3 hours under the condition a, the specimen was immersed in a solder bath at 260 ° C. for 20 seconds and the state of the test piece was visually observed. Was evaluated as x. Water absorption: A test piece cut to 50 mm × 50 mm was subjected to a moisture absorption treatment with a pressure cooker at 121 ° C. and 0.22 MPa for 3 hours, and the water absorption was calculated from the difference in weight before and after the moisture absorption treatment. Flame resistance: Evaluated according to the UL94 vertical test method. Table 1 shows the measurement and evaluation results.

[0045]

[Table 1]

From Table 1, it can be seen that Comparative Example 1 used bisphenol A type epoxy resin (DER331L) and brominated bisphenol A type epoxy resin (ESB400) as epoxy resins.
T), an epoxy resin (HP7200H) derived from a dicyclopentadiene-phenol polyadduct containing a dicyclopentadiene skeleton, and a brominated bisphenol A type epoxy resin (ESB400).
T), the relative dielectric constant, glass transition temperature (Tg), and water absorption are inferior. Comparative Example 2 is an epoxy resin in which only a bisphenol A type epoxy resin is blended, and an epoxy resin derived from a dicyclopentadiene-phenol polyadduct containing a dicyclopentadiene skeleton and a brominated bisphenol A type epoxy resin And the glass transition temperature (T
g), poor water absorption and flame resistance. Comparative Example 3 is a case where no epoxy resin is blended, and is inferior in solder heat resistance, water absorption and flame resistance. Comparative Example 4 is a laminate not using a cyanate ester resin, and has a high relative dielectric constant and a low glass transition temperature (Tg). In contrast to these comparative examples, it can be seen that the cyanate / epoxy resin composition of the present invention is excellent in glass transition temperature (Tg), dielectric constant, heat resistance and low in water absorption.

Examples 5 to 8 and Comparative Examples 6 to 10 Varnishes were prepared according to the formulations shown in Table 2 in the same manner as in Example 1, and then performed according to Example 1. Table 2 shows the test results.

[0048]

[Table 2]

As is evident from Table 2, the examples relating to the present invention are excellent in glass transition temperature (Tg), relative dielectric constant, heat resistance, water absorption and electrolytic corrosion resistance.

[0050]

The cyanate / epoxy resin composition of the present invention has excellent glass transition temperature (Tg), dielectric properties, heat resistance, and low water absorption. A prepreg or a laminate thereof, a metal foil-clad laminate, and a printed wiring board obtained by using the prepreg satisfy characteristics such as heat resistance, dielectric properties, and low hygroscopicity required for computer use and the like. Further, by adding an antioxidant to the above-mentioned cyanate / epoxy resin composition, the electrolytic corrosion resistance becomes excellent without impairing the above-mentioned properties.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Tomio Fukuda 1500 Oji Ogawa, Shimodate City, Ibaraki Prefecture Inside Hitachi Chemical Co., Ltd. (72) Inventor Masato Miyatake 1500 Oji Ogawa Shimodate City, Ibaraki Prefecture Within the Research Institute (72) Inventor Yasuyuki Mizuno 1500 Ogawa Oji, Shimodate-shi, Ibaraki Pref.Hitachi Chemical Industry Co., Ltd.

Claims (9)

[Claims] (A) a cyanate compound containing two or more cyanato groups in one molecule, (B) an epoxy resin,
(C) In a resin composition containing a curing accelerator as a main component, the epoxy resin is an epoxy resin derived from a dicyclopentadiene-phenol polyadduct having a dicyclopentadiene skeleton represented by the formula (1). A compound having a catalytic function of accelerating the curing reaction of a cyanate compound containing two or more cyanato groups in one molecule as a curing accelerator and a compound having a catalytic function of accelerating the curing reaction of an epoxy resin, respectively. A cyanate / epoxy resin composition used in combination. Embedded image (Where n represents 0 or a positive integer) 2. A compound having a catalytic function for accelerating the curing reaction of a cyanate compound containing two or more cyanato groups in one molecule is an organometallic salt or an organometallic complex. The cyanate / epoxy resin composition according to claim 1, wherein the compound having a promoting catalytic function is an imidazole compound. 3. The method according to claim 1, wherein the organometallic salt or the organometallic complex is iron,
The cyanate / epoxy resin composition according to claim 2, which is an organometallic salt or an organometallic complex of copper, zinc, cobalt, nickel, manganese, or tin. 4. (A) 50 to 250 parts by weight of an epoxy resin and (C) 0 to 100 parts by weight of a cyanate compound containing two or more cyanato groups per molecule. The cyanate / epoxy resin composition according to any one of claims 1 to 3, comprising 1 to 5 parts by weight. 5. The cyanate / epoxy resin composition according to claim 1, further comprising (D) an antioxidant. 6. The method according to claim 5, wherein (D) an antioxidant is contained in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of a cyanate compound containing two or more cyanato groups in one molecule. Cyanate epoxy resin composition. 7. A prepreg obtained by impregnating and drying a substrate with the cyanate / epoxy resin composition according to claim 1. 8. A metal foil-clad laminate obtained by laminating a metal foil on one or both surfaces of the prepreg or the laminate thereof according to claim 7, and subjecting the metal foil to heat and pressure molding. 9. A printed wiring board obtained by performing circuit processing on the metal foil of the metal foil-clad laminate according to claim 8.