JPH1112463A - Resin composition for printed circuit board, varnish, prepreg, and laminate for printed circuit board prepared therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compsn. excellent in curability, processibility, adhesiveness, heat resistance, flame resistance, and dielectric characteristics in a high-frequency zone by compounding, as essential ingredients, a mixture of specified cyanate compds. having -OCN groups, a monohydric phenol compd., and a flame retardant unreactive with the cyanate compds. SOLUTION: 100 pts.wt. cyanate compds. having two -OCN groups in the molecule and comprising a mixture of at least two compds. including an alkyl- subsd. cyanate compd. of formula I and a cyanate compd. of formula II having no substituent at the 2-position to the -OCN group is compounded with a monohydric phenol compd. (e.g. p-nonylphenol) pref. in an amt. of 5-30 pts.wt. and a flame retardant (e.g. tetrabromocyclooctane) pref. in an amt. of 5-200 pts.wt. In those formulas, R1 and R2 are each 1-4C alkyl; and R3 and R4 are each a (halogenated) alkylene, aralkylene, or alicyclic linking group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for printed wiring boards used for producing printed wiring boards having excellent dielectric properties and heat resistance, and varnishes, prepregs and laminates for printed wiring boards using the same. About.

[0002]

2. Description of the Related Art In recent years, a resin material having a low relative dielectric constant and a low dielectric loss tangent has been desired as a material for a printed wiring board used for high-frequency equipment in the communication field and the like. On the other hand, thermoplastic resins such as fluororesins and polyphenylene ethers with low relative permittivity and dielectric loss tangent have been used, but these are expensive, and they require high temperatures and high pressures during molding and have dimensional stability problems. However, there is a disadvantage that the adhesiveness to metal plating is poor. On the other hand, among thermosetting resin materials, resin materials such as a cyanate ester resin known as a resin having a low relative dielectric constant and a low dielectric loss tangent, and a BT (bismaleimide triazine) resin based on the same have been proposed. However, these resin materials alone have a lower reactivity than epoxy resins and the like, and thus have the disadvantage that high temperatures are required during molding to achieve good dielectric properties and a high glass transition temperature (Tg). In addition, it has been pointed out that the cured product is inferior in flame resistance and heat resistance after moisture absorption, and that it is fragile due to its rigid skeleton and easily cracks during processing.

In order to improve these problems, a method of using a glycidyl etherified product of phenol novolak described in JP-A-63-54419 in combination with a BT (bismaleimide triazine) resin or a cyanate ester resin has been proposed. Japanese Patent Application Laid-Open No. 3-84040 discloses a method of using a glycidyl etherified product of a phenol-added dicyclopentadiene polymer described in JP-A-2-214474.
And phenol-added butadiene polymers described in JP-A-5-310673, and polyvalent compounds such as bisphenol A described in JP-B-7-47637. Phenol compound, or Japanese Patent Publication No. 4-24370
Patent Document 2: Brominated bisphenol A and hydroxyl etherified product of brominated bisphenol A described in
Glycidyl etherified product of brominated phenol novolak described in JP-A-286723, JP-A-5-339342
Glycidyl etherified product of brominated bisphenol A disclosed in JP-A-7-207022, and BT (bismaleimide triazine) resin or cyanate ester resin such as a brominated maleimide compound described in JP-A-7-207022. A method of using a flame retardant in combination has been proposed.

[0004]

However, Japanese Patent Application Laid-Open No.
In the method of using an epoxy resin in combination with a cyanate ester resin as disclosed in JP-A-54419, JP-A-2-214474, and JP-A-3-84040, curability at low temperatures, processability, and after absorption of moisture. Although the defect relating to heat resistance is improved, Tg (glass transition temperature) is lowered and dielectric properties in the GHz band are deteriorated, so that it is insufficient for high frequency applications. Also, Japanese Patent Application Laid-Open No.
In the method using a polyhydric phenol compound as disclosed in Japanese Patent Publication No. 7-47637, the curability and processability are improved, but the Tg is lowered, the adhesive property, and the heat resistance during moisture absorption are reduced. However, there is a problem that the dielectric properties in the GHz band are deteriorated, and thus it cannot be used for high frequency applications. In addition, Japanese Patent Publication No. 4-24370,
JP-A-2-286723, JP-A-5-33934
No. 2, JP-A-7-207022 discloses a method in which a flame retardant is used in combination, although the flame resistance can be added, but the Tg is lowered, the heat resistance at the time of moisture absorption and the GH
There is a problem that the dielectric characteristics in the z band deteriorate. As described above, in the method using the epoxy resin, the polyhydric phenol compound and the reactive flame retardant in combination, the dielectric properties in the GHz band are not sufficient and the Tg is lowered.

[0005] Further, even if the cyanate ester resin alone is used, the problems are different depending on the kind as follows. Cyanate esters having a substituent such as an alkyl group at the 2-position of the cyanate group are susceptible to steric hindrance of the substituent during the curing reaction, and thus have low reactivity of the cyanate group. I need it. Conversely, a cyanate ester having no substituent at the 2-position of the cyanate group has high reactivity, but has a drawback that it has a high water absorption rate and is inferior in heat resistance at the time of moisture absorption, and has a low melt viscosity. Since the flow is very large, the moldability is inferior in that the range of molding conditions is narrow, and the workability such as drilling holes and punching the outer shape with a mold is inferior to the cyanate ester having a substituent at the 2-position of the cyanate group. There is a problem.

[0006] The present invention has been made in view of such a situation, without reducing the Tg, without impairing properties such as curability, workability, adhesion, flame resistance, heat resistance after moisture absorption, and the like.
It is an object of the present invention to provide a resin composition for a printed wiring board having excellent dielectric properties in a high frequency band, and a varnish, a prepreg and a laminate for a printed wiring board using the same.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a method comprising reacting (A) a cyanate compound having two cyanate groups in a molecule or a prepolymer thereof, (B) a monohydric phenol compound and (C) a cyanate compound. In a resin composition containing a flame retardant having no property as an essential component, (A) a cyanate compound having two cyanate groups in a molecule comprises an alkyl-substituted cyanate compound represented by the formula (1) and a compound represented by the formula ( It is a resin composition for printed wiring boards, which is a mixture of two or more kinds with a cyanate compound having no substituent at the 2-position of the cyanate group represented by 2).

Embedded image

Embedded image Further, the present invention is a resin varnish for a printed wiring board in which the resin composition for a printed wiring board is dissolved or dispersed in a solvent,
Further, after impregnating the substrate with the varnish for a printed wiring board, 80 to 20
It is a prepreg for a printed wiring board obtained by drying at 0 ° C. Furthermore, the present invention can also use this prepreg for printed wiring boards as a prepreg for interlayer connection of a multilayer printed wiring board, and also stacking a plurality of prepregs for a laminated board and further laminating a metal foil on the outside thereof. It is a laminate for printed wiring boards obtained by heating and pressing.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION (A) A cyanate compound having two cyanate groups in a molecule or a prepolymer thereof, which is used in the resin composition for a printed wiring board of the present invention, comprises:
A mixture of two or more kinds of an alkyl group-substituted cyanate compound represented by the formula (1) and a cyanate compound having no substituent at the 2-position of the cyanate group represented by the formula (2), Specific examples of the compound represented by 1) include bis (3,5-dimethyl-4-cyanatephenyl) methane and the like and prepolymers thereof. Specific examples of the compound represented by the formula (2) include 2,2-bis (4-
Cyanatephenyl) propane, bis (4-cyanatephenyl) ethane, 2,2-bis (4-cyanatephenyl) -1,1,1,3,3,3-hexafluoropropane, α, α′-bis (4 -Cyanate phenyl) -m
-Diisopropylbenzene, cyanate esterified products of phenol-added dicyclopentadiene polymers, and prepolymers thereof. Among them, 2,2-bis (4-cyanatephenyl) propane and α, α′-bis (4-cyanatephenyl) -m-diisopropylbenzene have relatively excellent low-temperature curability and the cured product has a dielectric property. It is particularly preferable because it is excellent.

The above-mentioned monomer (A) of a cyanate compound having two cyanate groups in the molecule has high crystallinity, and when these monomers are varnished with a solvent, the varnish may vary depending on the solid content concentration. May crystallize. Therefore, it is preferable to use the above-mentioned cyanate compound monomer after prepolymerization. Although the conversion of the cyanate group of the prepolymer is not particularly limited, it is usually 20 to 6%.
It is desirable to use a prepolymer converted within the range of 0% by weight.

(A) An alkyl group-substituted cyanate compound represented by the formula (1) used for a cyanate compound having two cyanate groups in the molecule or a prepolymer thereof and a cyanate group represented by the formula (2) The compounding ratio with the cyanate compound having no substituent at the 2-position is preferably Formula (1): Formula (2) = 30: 70 weight ratio to 70:30 weight ratio. When the mixing ratio of the formula (1) is less than 30% by weight, the water absorption is high and the heat resistance is reduced. When the mixing ratio is more than 70% by weight, the curability at low temperatures is inferior and the glass transition temperature is lowered. Not preferred.

Specific examples of the (B) monohydric phenol compound used in the resin composition for a printed wiring board of the present invention include p-nonylphenol, p-tert-butylphenol, p-tert-amylphenol, p-te
Examples thereof include an alkyl group-substituted phenol compound such as rt-octylphenol and a monohydric phenol compound represented by the formula (3). Examples of the monohydric phenol compound represented by the formula (3) include p- (α-cumyl) phenol, and p- (α-cumyl) phenol is preferable. Further, the monohydric phenol compound (B) may be used alone or in combination of two or more.

[0012]

Embedded image (In the formula, R ₅ and R ₆ represent a hydrogen atom or a methyl group, and may be the same or different, and m represents an integer of 1 to 2.)

In the present invention, the compounding amount of the (B) monohydric phenol compound is (A) a cyanate compound having two cyanate groups in a molecule or a prepolymer thereof.
It is preferable to mix in a range of 5 to 30 parts by weight with respect to parts by weight. More preferably, it is 7 to 30 parts by weight. 5
If the amount is less than part by weight, the dielectric properties tend to deteriorate, which is not desirable. If the amount exceeds 30 parts by weight, the storage stability of the varnish when varnished tends to decrease, which is not desirable.

Specific examples of the flame retardant having no reactivity with the cyanate compound (C) used in the resin composition for a printed wiring board of the present invention include 1,2-dibromo-4-.
There are aliphatic ring-type flame retardants such as (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, and hexabromocyclododecane, and examples are preferable. Further, a heterocyclic flame retardant represented by the formula (4) may be mentioned, and examples of the heterocyclic flame retardant represented by the formula (4) include 2,4,6
-Tris (tribromophenoxy) -1,3,5-triazine and the like, and an example is preferable. The flame retardant having no reactivity with the (C) cyanate compound is (A)
5 to 20 parts by weight based on 100 parts by weight of a cyanate compound having two cyanate groups in the molecule or a prepolymer thereof.
It is preferable to mix in a range of 0 parts by weight. Preferably, it is 5 to 100 parts by weight. If it is less than 5 parts by weight, the flame retardant effect is poor, and if it exceeds 200 parts by weight, the heat resistance is undesirably reduced.

[0015]

Embedded image (Where l, m, and n represent integers of 1 to 5 and may be the same or different, respectively)

In the resin composition for a printed wiring board of the present invention, a curing accelerator for accelerating the curing reaction is used. Specific examples of the curing accelerator include organic metal salt compounds and organic metal complexes such as cobalt, manganese, tin, nickel, zinc, and copper. In particular, organic cobalt salt compounds such as cobalt 2-ethylhexanoate and cobalt naphthenate are preferred. The organometallic salt compounds may be used alone or in combination of two or more. The compounding amount of the curing accelerator is as follows: (A) a cyanate compound having two cyanate groups in the molecule or a prepolymer thereof.
The amount is 0.01 to 3 parts by weight, more preferably 0.1 to 3 parts by weight, within a range that does not deteriorate the mixing effect and the physical properties of the cured product.
02 to 0.5 parts by weight.

The resin composition for a printed wiring board of the present invention may further contain, if necessary, a filler and other additives. As the filler, usually, an inorganic filler is suitably used, and specific examples thereof include fused silica, glass, alumina, titania, zircon, calcium carbonate, and the like.
Examples thereof include calcium silicate, magnesium silicate, aluminum silicate, silicon nitride, boron nitride, beryllia, zirconia, barium titanate, potassium titanate, and calcium titanate.

The resin composition for a printed wiring board of the present invention is subjected to heat curing to provide a printed wiring board having excellent dielectric properties and heat resistance. That is, the resin composition for a printed wiring board of the present invention is dissolved and dispersed in a solvent to form a varnish once, impregnated into a substrate such as a glass cloth, and dried to prepare a prepreg. Next, a desired number of the prepregs are laminated with a metal foil on the upper and lower sides or on one side and heat-molded to form a printed wiring board or a metal-clad laminate. Here, drying refers to removing the solvent when a solvent is used, or eliminating fluidity at room temperature when no solvent is used.

When varnishing the resin composition for a printed wiring board of the present invention, the solvent is not particularly limited, but specific examples thereof include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, and the like. Aromatic hydrocarbons such as xylene, methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, esters such as ethyl acetate, N-methylpyrrolidone, formamide, N-methylformamide;
Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol, triethylene glycol Alcohols such as monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, and dipropylene glycol monopropyl ether are used. These solvents may be used alone or in combination of two or more.

The above-mentioned resin varnish for printed wiring boards is impregnated into a base material used for a laminated board such as glass woven fabric or glass non-woven fabric, plastic woven fabric or plastic non-woven fabric, or paper, and then dried at 80 to 200 ° C. To make a prepreg for printed wiring boards. When used as a prepreg for interlayer bonding of a multilayer printed wiring board, the resin content in the prepreg is increased. In addition, when a laminated board for a printed wiring board is required, depending on the required dielectric properties, if a value of a dielectric constant or a dielectric loss tangent is required to be small, the printed wiring board of the present invention having excellent dielectric properties is required. In order to increase the resin composition, the resin content is increased.

A plurality of prepregs for printed wiring boards are laminated, and a metal foil is further laminated on the outside of the prepreg, and heated and pressed to form a laminated board for printed wiring boards.

In general, the dielectric properties of a cured resin are affected by the molecular structure, that is, the amount and strength of the polar group in the molecule, the mobility of the molecular skeleton, and the like. Originally, a cured product of a cyanate ester has a low dielectric constant and a low dielectric loss tangent because it has a triazine skeleton having a low polarity, rigid and symmetric structure. But,
Reactive flame retardant with reactivity with polyfunctional epoxy resin, polyhydric phenolic compound and cyanate group to cyanate ester to improve moldability, curability, processability and heat resistance during moisture absorption and to add flame resistance In a conventional resin composition in which is used in combination, a high polar group is generated in a structure other than a triazine ring by a reaction with a cyanate group, or fluidity is lost due to the progress of a curing reaction, and the reaction is left unreacted. Since the number of functional groups increases, Tg and heat resistance decrease, and the relative dielectric constant and dielectric loss tangent increase. On the other hand, the resin composition for a printed wiring board of the present invention does not use a polyfunctional epoxy resin or a polyhydric phenol compound and thus does not have the above-described problem, and has a substituent at the 2-position of the cyanate group. Combination use of a cyanate compound having a cyanate compound or a prepolymer thereof and a cyanate compound having no substituent at the 2-position of the cyanate group or a prepolymer thereof has a reduced curability due to steric hindrance, and has low water absorption. And good moldability and workability. The phenolic compound used in the present invention is a phenolic compound having high reactivity with a cyanate group and promoting the formation of a triazine ring among monovalent phenolic compounds. In addition, the flame retardant used in the present invention is a flame retardant having a low polarity structure and having no reactivity to a cyanate group. Can be added. Therefore,
The obtained cured product has high curability and Tg, excellent moldability,
It has processability, adhesiveness, water absorption, heat resistance and flame resistance, and has a low dielectric constant and a low dielectric loss tangent.

[0023]

The present invention will be described in detail below, but the present invention is not limited to these.

Example 1 (A) As a cyanate compound having two cyanate groups in a molecule or a prepolymer thereof, an alkyl-substituted cyanate compound, bis (3,5-dimethyl-
Prepolymer of 4-cyanatephenyl) methane (Aro
cyM-30 (trade name, manufactured by Asahi Chiba Corporation) and a prepolymer of 2,2-bis (4-cyanatophenyl) propane (Arocy B-), which is a cyanate compound having no substituent at the 2-position of the cyanate group 30, Asahi Ciba Co., Ltd.), (B) monohydric phenol compounds
As a flame retardant having no reactivity with p-nonylphenol and (C) cyanate compounds, 1,2-dibromo-4
-(1,2-dibromoethyl) cyclohexane (SAY
TEX BCL-462 (trade name, manufactured by Albemarle Co., Ltd.) in toluene at the compounding amounts shown in Table 1, and 0.1 parts by weight of cobalt naphthenate with respect to 100 parts by weight of a cyanate compound as a curing accelerator. To prepare a varnish for printed wiring boards having a nonvolatile content of 65% by weight.

Example 2 Bis (3,5-dimethyl-4)
-Cyanatephenyl) methane prepolymer and 2,2-
Bis (4-cyanatephenyl) -1,1,1,3,
Methyl ethyl ketone solution of a prepolymer of 3,3-hexafluoropropane (Arocy F-40S, trade name, manufactured by Asahi Ciba Co., Ltd.), p-tert-butylphenol and tetrabromocyclooctane (SAYTEX BC-
48, trade name of Albemarle Co., Ltd.) in toluene at the compounding amounts shown in Table 1 and further, as a curing accelerator, 0.1 part by weight of cobalt naphthenate with respect to 100 parts by weight of a cyanate compound. A varnish for printed wiring boards having a nonvolatile content of 65% by weight was produced.

Example 3 Bis (3,5-dimethyl-4)
-Cyanate phenyl) methane prepolymer and α, α '
-Bis (4-cyanatephenyl) -m-diisopropylbenzene (RTX-366, trade name of Asahi Ciba Co., Ltd.), p-tert-octylphenol and hexabromocyclododecane (CD-75P, trade name of Great Lakes Co.) Was dissolved in toluene in the amounts shown in Table 1, and 0.1 parts by weight of cobalt naphthenate was added as a curing accelerator to 100 parts by weight of a cyanate compound to obtain a printed wiring having a nonvolatile content of 65% by weight. A plate varnish was prepared.

Example 4 In Example 1, p-nonylphenol was added to p- (α-cumyl) phenol and 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane was added to brominated triphenylcyan. Nurate (Piroguard SR-245, trade name of Daiichi Kogyo Seiyaku Co., Ltd.)
A varnish for printed wiring boards having a nonvolatile content of 65% by weight was prepared in the same manner as in Example 1 except that the compounding amounts shown in Table 1 were used instead.

Comparative Example 1 The procedure of Example 1 was repeated, except that the prepolymer of bis (3,5-dimethyl-4-cyanatephenyl) methane was dissolved in toluene in the amount shown in Table 1. Thus, a varnish for printed wiring boards having a nonvolatile content of 65% by weight was produced.

Comparative Example 2 In Comparative Example 1, 2,2-
The prepolymer of bis (4-cyanatephenyl) propane is converted to bis (3,5-dimethyl-4-cyanatephenyl)
In the same manner as in Comparative Example 1 except that the methane prepolymer was dissolved in toluene at the compounding amount shown in Table 1, the non-volatile content was 65%.
By weight, a varnish for a printed wiring board was prepared.

Comparative Example 3 In Comparative Example 1, 1,2-
Dibromo-4- (1,2-dibromoethyl) cyclohexane is converted to a brominated bisphenol A type epoxy resin (ESB
A varnish for a printed wiring board having a nonvolatile content of 65% by weight was prepared in the same manner as in Comparative Example 1 except that 400T (trade name, manufactured by Sumitomo Chemical Co., Ltd.) was dissolved in toluene at the compounding amount shown in Table 1.

Comparative Example 4 In Comparative Example 1, except for p-nonylphenol, 1,2-dibromo-4- (1,2
A varnish for a printed wiring board having a nonvolatile content of 65% by weight was prepared in the same manner as in Comparative Example 1, except that -dibromoethyl) cyclohexane was dissolved in toluene at the compounding amount shown in Table 1 in place of brominated bisphenol A (TBA). .

Comparative Example 5 In Comparative Example 1, p-nonylphenol was converted to a phenol-added butadiene polymer (P
P700-300, trade name of Nippon Petrochemical Co., Ltd.)
And 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane was replaced with a brominated phenol novolak type epoxy resin (BREN-S, trade name, manufactured by Nippon Kayaku Co., Ltd.), and the compounding amount shown in Table 1 was used. A varnish for printed wiring boards having a nonvolatile content of 65% by weight was prepared in the same manner as in Comparative Example 1 except that the varnish was dissolved in toluene.

[0033]

[Table 1]

The varnish for a printed wiring board obtained in each of Examples and Comparative Examples was impregnated into a glass cloth (E glass, basis weight 210 g / m ² ) having a thickness of 0.2 mm, and heated at 140 ° C. for 10 minutes. A prepreg for a printed wiring board having a resin content of about 41% by weight was obtained. Next, four pieces of the obtained printed wiring board prepregs were stacked, and copper foil having a thickness of 18 μm was stacked on both sides thereof at 170 ° C.
After press molding for 60 minutes under the condition of 2.5 MPa, 20
Heat-treated at 0 ° C. for 120 minutes and heat-treated at 230 ° C. for 120 minutes.
mm was obtained.

The obtained laminate for a printed wiring board was measured for dielectric properties, solder heat resistance, Tg (glass transition temperature), and copper foil peeling strength. Table 2 shows the results.
The evaluation of the measurement items other than the dielectric properties and Tg was 23
A printed wiring board laminate subjected to heat treatment at 0 ° C. was used.

The test method is as follows. 1 MHz relative dielectric constant (εr) and dielectric loss tangent (tan)
δ): Measured according to JIS C-6481. A relative dielectric constant (εr) of 1 GHz and a dielectric loss tangent (tan)
δ): Measured by a triplate structure straight line resonator method. Tg: The copper foil was removed by etching and measured by TMA (thermomechanical analysis). -Solder heat resistance: PCT (121
(0.2 ° C., 0.22 MPa), and immersed in molten solder at 260 ° C. for 20 seconds to examine the appearance. The number of abnormalities in the table means that there is no occurrence of measling and blistering, and the number for the test number (denominator) is (numerator). -Flame resistance: Measured according to the UL-94 vertical test method. -Copper foil peel strength: Measured in accordance with JIS C-6481. Water absorption: The copper foil was removed by etching and calculated from the weight change before and after the PCT treatment. Workability: The copper foil was removed by etching, and after punching the outer shape with a mold, the appearance of the cut portion was examined. Good in the table means that there is no occurrence of peeling, whitening (cracks), and fluff.

[0037]

[Table 2]

As is clear from Table 2, the laminated boards for printed wiring boards using the resin compositions for printed wiring boards of Examples 1 to 4 all have low water absorption, workability, and solder heat resistance during moisture absorption. And copper foil peeling strength are good. In addition, 1GHz
Dielectric constant and dielectric loss tangent at 200 ° C. and 230 ° C. are almost the same as those of post-heat treated products, and Tg is 200 ° C.
It shows almost the same high value as that of the post-heat treated products at 230 ° C. and is excellent in curability.

On the other hand, the printed wiring board laminate of Comparative Example 1 is inferior in workability to the printed wiring board laminates of Examples 1 to 4, and has a relative dielectric constant of 1 GHz, a dielectric loss tangent and water absorption. The rate is somewhat high. The laminated board for a printed wiring board of Comparative Example 2 had 20
The dielectric properties and Tg of the post-heat-treated product at 0 ° C. are slightly inferior to those of the post-heat-treated product at 230 ° C., and the curability is inferior to those of the examples. The copper-clad laminates of Comparative Examples 3 to 5 have low copper foil peeling strength and low solder heat resistance during moisture absorption, and have a high relative dielectric constant, dielectric loss tangent and water absorption of 1 GHz.

[0040]

As described above, the resin composition for a printed wiring board, the varnish, and the prepreg and laminate using the same according to the present invention, when formed into a printed wiring board, have good moldability, adhesiveness, and moisture absorption. It has good heat resistance, low relative dielectric constant and low dielectric loss tangent in a high frequency band, and is suitable as a resin composition for a printed wiring board used for a printed wiring board corresponding to a device handling a high frequency signal.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5/3477 C08K 5/3477 C09D 179/00 C09D 179/00 H05K 1/03 610 H05K 1/03 610H

Claims (15)

[Claims] (A) a cyanate compound having two cyanate groups in a molecule or a prepolymer thereof, (B)
In a resin composition containing, as an essential component, a monohydric phenol compound and a flame retardant having no reactivity with the (C) cyanate compound, the (A) cyanate compound having two cyanate groups in the molecule is represented by the formula (1) Wherein the mixture is a mixture of two or more of an alkyl group-substituted cyanate compound represented by formula (1) and a cyanate compound having no substituent at the 2-position of the cyanate group represented by formula (2). Resin composition for wiring board. Embedded image (Wherein, R ₁ and R ₂ each represent a lower alkyl group having 1 to 4 carbon atoms, which may be the same or different. R ₃ is a divalent group and is an alkylene group. Group, a halogenated alkylene group, an aralkylene group, and an alicyclic bonding group.) (In the formula, R ₄ is a divalent group, and represents an alkylene group, a halogenated alkylene group, an aralkylene group, or an alicyclic bonding group.) 2. (A) 5 to 30 parts of (B) a monohydric phenol compound per 100 parts by weight of a cyanate compound having two cyanate groups in a molecule or a prepolymer thereof.
The resin composition for a printed wiring board according to claim 1, wherein 5 to 200 parts by weight of a flame retardant having no reactivity with the (C) cyanate compound is mixed. 3. An alkyl-substituted cyanate compound represented by the formula (1) used for a cyanate compound having two cyanate groups in the molecule or a prepolymer thereof, and a cyanate represented by the formula (2): The compound of the formula (1): formula (2) = 30: 70 weight ratio to 70:30 weight ratio with a cyanate compound having no substituent at the 2-position of the group. 3. The resin composition for a printed wiring board according to 2. 4. The method according to claim 1, wherein (A) the cyanate compound having two cyanate groups in the molecule or the alkyl-substituted cyanate compound represented by the formula (1) used in the prepolymer thereof is bis (3,5-dimethyl- The resin composition for a printed wiring board according to any one of claims 1 to 3, wherein the resin composition is (4-cyanatephenyl) methane. (A) a cyanate compound having two cyanate groups in the molecule or a cyanate compound having no substituent at the 2-position of the cyanate group represented by the formula (2) used in the prepolymer thereof; The resin composition for a printed wiring board according to any one of claims 1 to 4, which is 2,2-bis (4-cyanatephenyl) propane. (A) a cyanate compound having two cyanate groups in the molecule or a cyanate compound having no substituent at the 2-position of the cyanate group represented by the formula (2) used for the prepolymer thereof; The resin composition for a printed wiring board according to any one of claims 1 to 4, wherein the resin composition is α, α'-bis (4-cyanatephenyl) -m-diisopropylbenzene. 7. The resin composition for a printed wiring board according to claim 1, wherein (B) the monohydric phenol compound is an alkyl group-substituted phenol compound. 8. An alkyl group-substituted phenol compound,
p-nonylphenol, p-tert-butylphenol, p-tert-amylphenol and p-tert
The resin composition for a printed wiring board according to claim 7, wherein the resin composition is one kind or two or more kinds selected from octylphenol. 9. The method according to claim 1, wherein the monohydric phenol compound (B) is one or more monohydric phenol compounds represented by the formula (3). A resin composition for a printed wiring board. Embedded image (In the formula, R ₅ and R ₆ represent a hydrogen atom or a methyl group, and may be the same or different, and m represents an integer of 1 to 2.) 10. The resin composition for a printed wiring board according to claim 9, wherein the monohydric phenol compound represented by the formula (3) is p- (α-cumyl) phenol. 11. The flame retardant having no reactivity with the cyanate compound (C) is 1,2-dibromo-4- (1,2-
The resin for a printed wiring board according to any one of claims 1 to 10, wherein the resin is at least one kind of an aliphatic cyclic flame retardant selected from dibromoethyl) cyclohexane, tetrabromocyclooctane, and hexabromocyclododecane. Composition. 12. The flame retardant having no reactivity with the cyanate compound (C) is one or more heterocyclic flame retardants represented by the formula (4).
0. The resin composition for a printed wiring board according to any one of 0. Embedded image (Where l, m, and n represent integers of 1 to 5 and may be the same or different, respectively) 13. A resin varnish for printed wiring boards, wherein the resin composition for printed wiring boards according to any one of claims 1 to 12 is dissolved or dispersed in a solvent. 14. A prepreg for a printed wiring board obtained by impregnating a substrate with the resin varnish for a printed wiring board according to claim 13 and drying at 80 to 200 ° C. 15. A laminate for a printed wiring board obtained by laminating a plurality of the prepregs for a printed wiring board according to claim 14, further laminating a metal foil on the outside thereof, and applying heat and pressure.