JP3382510B2 - Modified cyanate ester resin varnish for printed wiring boards and method for producing prepreg for laminated board and metal-clad laminate using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printed wiring for use in a high-speed computer or the like, in which a wireless communication-related terminal device or antenna required for low loss in a high frequency band and an operating frequency of a microprocessor exceed several hundred MHz. TECHNICAL FIELD The present invention relates to a modified cyanate ester resin varnish for a printed wiring board, which is suitable for producing a board for a board, a prepreg for a laminate using the varnish, and a method for producing a metal-clad laminate.

[0002]

2. Description of the Related Art In the advanced information society, it is necessary to process a large amount of data at a high speed, and in computers and information equipment terminals, the frequency of signals is increasing. However, the electric signal has a property that the transmission loss increases as the frequency increases, and thus there is a strong demand for the development of a low-loss printed wiring board compatible with higher frequencies.

The transmission loss in a printed wiring board is caused by the wiring (conductor).
The conductor loss is determined by the shape, the skin resistance, the characteristic impedance, and the like, and the dielectric loss is determined by the dielectric characteristics of the insulating layer (dielectric) around the wiring. In a high frequency circuit, the power loss is greatly affected by the dielectric loss. Therefore, in order to reduce the transmission loss of the high frequency circuit, it is considered necessary to reduce the dielectric constant and the dielectric loss tangent (tan δ) of the printed wiring board substrate (particularly insulating resin). For example, in equipment related to mobile communication that handles high-frequency signals, a substrate having a low dielectric loss tangent is strongly desired in order to reduce transmission loss in the quasi-microwave band (1 to 3 GHz) as the frequency of signals increases. There is.

In electronic information devices such as computers, in order to process a large amount of information in a short time, a high-speed microprocessor having an operating frequency exceeding 200 MHz has been developed and the frequency of signals has been increased. In devices handling such high-speed pulse signals, delay on the printed wiring board has become a problem. Since the signal delay time in a printed wiring board increases in proportion to the square root of the relative permittivity εr of the insulator around the wiring, a wiring board used for a computer or the like requires a resin for a substrate having a low permittivity.

As a resin composition for improving the high frequency characteristics of a printed wiring board in response to the high frequency of the signal as described above, a composition of cyanate ester resin having the lowest dielectric constant among thermosetting resins is disclosed in Japanese Patent Publication No. There is a method using a cyanate ester / epoxy resin composition disclosed in Japanese Patent Publication No. 46-41112 and a bismaleimide / cyanate ester / epoxy resin composition disclosed in Japanese Patent Publication No. 52-31279.

In order to improve high frequency characteristics by using a thermoplastic resin, a polyphenylene ether resin (PPO or PP disclosed in Japanese Patent Publication No. 5-77705) is disclosed.
E) and a crosslinkable polymer / monomer resin composition, and a resin composition of a polyphenylene ether resin having a specific curable functional group and a crosslinkable monomer as disclosed in Japanese Patent Publication No. 9-92533. Among heat resistant thermoplastic resins, there is a method of using a polyphenylene ether resin composition having good dielectric properties.

Further, a cyanate ester disclosed in Japanese Examined Patent Publication No. 63-33506 discloses a cyanate ester resin having a low dielectric constant and a polyphenylene ether resin having good dielectric properties for improving high frequency characteristics. / A resin composition of bismaleimide and a polyphenylene ether resin, and a method of using a resin composition of a phenol-modified resin / cyanate ester reaction product and a polyphenylene ether resin disclosed in JP-A-5-311071. Further, as a heat-resistant molding material having good high frequency characteristics, there is a resin composition obtained by kneading a polyphenylene ether resin with a cyanate ester resin as disclosed in Japanese Patent Publication No. 61-18937.

[0008]

[Problems to be Solved by the Invention] Japanese Patent Publication No. 4-4111
The methods disclosed in Japanese Patent Publication No. 2 and Japanese Patent Publication No. 52-31279 have a problem that the high frequency characteristics are insufficient because they contain a thermosetting resin other than the cyanate ester resin although the dielectric constant is slightly lowered. there were.

Japanese Patent Publication No. 5-77705 and Japanese Patent Publication No. 6-9
Although the method disclosed in Japanese Patent No. 2533 has improved dielectric properties, it has a problem that the melt viscosity of the resin composition is high and the fluidity is insufficient because it is mainly composed of polyphenylene ether resin which is originally a thermoplastic polymer. It was Therefore, the moldability is poor and unsuitable for producing a multilayer printed wiring board which requires high temperature and high pressure at the time of press-forming a laminated board and needs to fill the grooves between fine circuit patterns.

JP-B-63-33506 and JP-A-5-
In the method disclosed in Japanese Patent No. 311071, since the thermosetting resin used in combination with the polyphenylene ether resin is a bismaleimide / cyanate ester resin or a phenol modified resin / cyanate ester reaction product, the dielectric characteristics are slightly improved, but the high frequency characteristics are There was a problem that it was still insufficient. It should be noted that if the compounding amount of the polyphenylene ether resin is increased in order to improve the high frequency characteristics, the melt viscosity of the resin composition becomes high and the flowability becomes insufficient and the moldability is poor as in the case of the aforementioned polyphenylene ether resin composition. There was a problem.

A resin composition obtained by kneading a polyphenylene ether resin with a cyanate ester resin disclosed in Japanese Patent Publication No. 61-18937 has good dielectric properties and, when modified with a cyanate ester resin, has a low melt viscosity. Although the moldability of the composition is also relatively good, when a cyanate ester is used alone as a curable component, the dielectric properties of the resin cured product tend to have a high dielectric loss tangent relative to the value of the dielectric constant. However, there is a problem in that the transmission loss of can not be reduced sufficiently. Further, if the amount of cyanate ester is reduced (the amount of polyphenylene ether resin is increased) in order to lower the dielectric loss tangent, the melt viscosity of the resin composition is increased and the fluidity is increased as in the case of the polyphenylene ether resin composition described above. There was a problem that the formability was poor due to the lack of it.

In view of such a situation, the present inventors have used a method in which a composition obtained by previously modifying a specific cyanate ester resin with a monohydric phenol compound is used as a part or the whole of a matrix resin (Japanese Patent Application No. Hei 9 (1999) -96242). -80033) was proposed. However, certain cyanate ester resins are
Although it was possible to obtain a resin composition having good high-frequency characteristics by modifying it with a dihydric phenol compound, there was a problem that the specific cyanate ester resin used was special and expensive.

The present invention has good heat resistance, has moldability and workability similar to those of conventional thermosetting resin laminates such as epoxy resin, and has low dielectric properties, especially dielectric loss tangent in a high frequency band. Provided are a modified cyanate ester resin varnish for a printed wiring board capable of producing a high-density multilayer wiring board excellent in low loss property, a prepreg for a laminated board using the same, and a method for producing a metal-clad laminated board.

[0014]

The present invention provides (A) a cyanate ester compound represented by formula (1), (B)
Monohydric phenol compound represented by formula (2), (C) polyphenylene ether resin, (D) flame retardant having no reactivity with cyanate ester compound, (E) metal-based reaction catalyst, (F) aromatic A modified cyanate ester resin varnish for a printed wiring board of a modified cyanate ester resin containing a hydrocarbon solvent and a (G) ketone solvent as essential components, a prepreg for a laminated board using the same, and a method for producing a metal-clad laminated board. .

[0015]

[Chemical 4]

[0016]

[Chemical 5]

In addition to the above, the present invention provides (A) formula (1)
It is preferable to mix 4 to 30 parts by weight of the monohydric phenol compound (B) represented by the formula (2) with 100 parts by weight of the cyanate ester compound represented by. A method for producing a modified cyanate ester resin varnish for a printed wiring board, a prepreg for a laminate using the same, and a metal-clad laminate, which are excellent in heat resistance.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Dielectric properties of polymer materials and the like are greatly affected by orientation polarization of dipoles. Therefore, by reducing polar groups in the molecule, the dielectric constant can be lowered and the mobility of polar groups can be suppressed. As a result, the dielectric loss tangent can be lowered. Cyanate ester resin has a symmetry and a rigid triazine structure at the time of curing even though it has a cyanato group having a strong polarity, so that a cured product having the lowest dielectric constant and dielectric loss tangent as a thermosetting resin can be obtained. There is.

However, in the actual curing reaction, it is impossible that all the cyanato groups in the cyanate ester resin react to form a triazine structure, and the reaction system becomes fluid with the progress of the curing reaction. Is lost and remains in the system as an unreacted cyanato group.
As a result, until now, only a cured product having a higher dielectric constant or dielectric loss tangent than the original cured product was obtained.

On the other hand, in the resin varnish for a printed wiring board of the present invention, by mixing (B) a monohydric phenol compound in an appropriate amount, the unreacted cyanato group is converted to imide carbonate to reduce its polarity. This is to reduce the dielectric constant and dielectric loss tangent of the cured product. As a material used for this purpose, a compound having a high reactivity with a cyanato group, a monofunctional compound having a relatively low molecular weight, and a good compatibility with a cyanate ester resin (having a similar molecular structure) is suitable. It is believed that The monovalent phenol compound used in the modified cyanate ester resin varnish for a printed wiring board of the present invention is a compound specified for such reasons.

Conventionally, as a cocatalyst for the trimerization reaction (formation of triazine ring) of cyanate ester, a phenol compound such as nonylphenol is cyanate ester 100.
About 1 to 2 parts by weight was used with respect to parts by weight. However, since the compounding amount was a catalytic amount, the above-described effect of reacting with unreacted cyanato groups to reduce the polarity was not recognized. However, as a result of the inventors' studying the blending amount of the phenol compound, it was confirmed that the blending amount of the phenol compound in a larger amount than the conventional one lowered the dielectric constant and dielectric loss tangent of the cured product, and the specific monohydric phenols It has been found that the use of the compound can suppress a decrease in heat resistance due to an increase in the compounding amount. Therefore, according to the method of the present invention, a conventional cured product of a cyanate ester resin alone, a conventional epoxy resin or a polyhydric phenol (which deteriorates the dielectric properties because one hydroxyl group is likely to remain as an unreacted group) and It has become possible to obtain a cured product having a lower dielectric constant and dielectric loss tangent than a cured product of a resin containing bismaleimide or the like.

Therefore, in the resin varnish for a printed wiring board of the present invention, the blending amount of the monohydric phenol compound is important. That is, when the blending amount is small, it is not possible to reduce the polarity by reacting with all the cyanato groups remaining as unreacted, and when the blending amount is larger than the necessary amount, oneself remains as unreacted, and This is because the dielectric properties of the cured product are deteriorated depending on the polarity of the hydroxyl group.

Further, in the modified cyanate ester resin varnish for printed wiring board of the present invention, the dielectric property is improved by blending (C) polyphenylene ether resin, which is a thermoplastic resin having good dielectric properties, with the above modified cyanate ester resin. I am trying to The cyanate ester resin and the polyphenylene ether resin are originally incompatible systems and it is difficult to obtain a uniform resin. However, according to the method found by the present inventors, (A) a cyanate ester compound and ( B) When the reaction of a monohydric phenol compound is carried out in a solvent solution of polyphenylene ether resin, so-called "semi-IPN (interpenetrating polymer network)" is obtained.
It was found that a "resinized resin" was produced and a uniform resin solution was obtained.

That is, in the modified cyanate ester resin varnish for a printed wiring board of the present invention, (F) an aromatic hydrocarbon solvent is used to heat-dissolve (C) a polyphenylene ether resin, and (A) is added to the solution. Oligomerization of cyanate ester compound and (A) cyanate ester compound and (B) monohydric phenol compound are subjected to imidocarbonation reaction to produce a compatibilizing resin of modified cyanate ester resin and polyphenylene ether resin. There is. Regarding compatibilization at this time, it is unlikely that the modified cyanate ester resin and the polyphenylene ether resin form a chemical bond, and instead, a part of the modified cyanate ester resin is entangled in the molecular chain of the polyphenylene ether resin. However, it is considered that so-called "semi-IPN resin" is being produced due to progress of oligomerization. In this case, in order to promote the entanglement of the molecular chain, the molecular chain of the polyphenylene ether resin being dissolved is widened, and a part of the modified cyanate ester resin is easily entangled in the molecular chain of the polyphenylene ether resin. It is preferable to use (F) an aromatic hydrocarbon solvent, which is a good solvent of (4), which also dissolves the modified cyanate ester resin at the same time, as the reaction solvent.

However, a high molecular weight solution dissolved in a good solvent generally has the property of increasing its viscosity, and the resin varnish of the present invention also has an extremely high viscosity in the state of (F) aromatic hydrocarbon type solution. Very high and high-concentration solutions become close to solids. Therefore, only a low concentration of resin varnish for printed wiring board can be obtained, and as a result, the amount of resin adhered to the prepreg becomes low, which causes a problem that the laminate has a defective scraping (insufficient resin) after press molding. .

Therefore, the present inventors have found that in order to obtain a high-concentration modified cyanate ester resin varnish for printed wiring boards,
A method of introducing (G) a ketone solvent into a compatibilizing resin solution of a modified cyanate ester resin and a polyphenylene ether resin produced in an aromatic hydrocarbon-based solution, stirring and suspending the solution to reduce the viscosity is adopted, After producing a (F) aromatic hydrocarbon solvent solution of a compatibilizing resin of a high-concentration modified cyanate ester resin and a polyphenylene ether resin,
(G) A modified cyanate ester resin varnish for a printed wiring board, which can produce a prepreg with a relatively high concentration and a high resin adhesion amount, can be obtained by adding and stirring a ketone solvent and suspending it. Got knowledge that can be obtained.

The flame retardant used in the modified cyanate ester resin varnish for printed wiring boards of the present invention is
It is essential that the (A) cyanate ester compound and the (B) monohydric phenol compound do not have reactivity with the cyanate ester compound so as not to hinder the reaction, and the compound is a hydrocarbon-based low-polarity compound and thus cured. It rarely deteriorates the dielectric properties of the product. In addition, another type of specified flame retardant has a triazine structure similar to that of a cured product of cyanate ester even if it is a compound other than a hydrocarbon-based compound, so it is easily compatible with a cured product of cyanate ester resin, and has heat resistance and dielectric properties. The flame resistance can be imparted without deteriorating.

A modified cyanate ester resin varnish for a printed wiring board of the present invention and a prepreg for a laminated board using the varnish,
The method for producing a metal-clad laminate is (A) a cyanate ester compound represented by the formula (1), (B) a monohydric phenol compound represented by the formula (2), (C) a polyphenylene ether resin, (D). Modified cyanate ester for printed wiring board containing a flame retardant having no reactivity with cyanate ester compounds, (E) metal reaction catalyst, (F) aromatic hydrocarbon solvent and (G) ketone solvent as essential components In a resin varnish, (C) polyphenylene ether resin is heated and dissolved in (F) aromatic hydrocarbon solvent, and then (A) cyanate ester compound and (B) are dissolved in the solution.
After reacting the monohydric phenol compound in the presence of the (E) metal-based reaction catalyst to prepare a compatibilized resin solution of the modified cyanate ester resin and the polyphenylene ether resin,
A modified cyanate for a printed wiring board, which is excellent in high-frequency characteristics and is capable of increasing the concentration of a modified cyanate ester resin composition obtained by suspending a compatibilizing resin by adding (G) a ketone solvent to a reaction solution and stirring it. It is an ester resin varnish. Then, after impregnating the varnish into the base material, the base material is dried at 80 to 200 ° C. to produce a prepreg for a laminated plate, one or more prepregs for the laminated plate are stacked, and a metal foil is further provided on the upper or lower surface or one surface thereof. This is a method for producing a metal-clad laminate obtained by stacking and heating under pressure.

The cyanate ester compound (A) in the present invention is a cyanate ester compound having two cyanato groups in one molecule as shown by the formula (1).
Examples of the compound represented by the formula (1) include bis (4
-Cyanatophenyl) ethane, 2,2-bis (4-cyanatophenyl) propane, bis (3,5-dimethyl-4)
-Cyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, α, α'-bis (4-cyanatophenyl)- Examples include m-diisopropylbenzene, a cyanate esterified product of a phenol-added dicyclopentadiene polymer, and the like. Among them, 2,2-bis (4-cyanatophenyl) propane and bis (3,5-dimethyl-4)
-Cyanatophenyl) methane and the like are more preferable. Moreover, as the (A) cyanate ester compound, one kind may be used alone, or two or more kinds may be mixed and used.

The monohydric phenol compound (B) in the present invention is an alkyl-substituted phenol compound represented by the formula (2), and a compound having good heat resistance is preferable. Examples of the compound represented by the formula (2) include p-tert-butylphenol, p-tert-amylphenol and p-tert-amylphenol.
-Tert-octylphenol is mentioned, and among them, p-tert-octylphenol is more preferable.
As the monohydric phenol compound (B), one of the above compounds may be used alone, or two or more thereof may be mixed and used.

The blending amount of the (B) monohydric phenol compound in the present invention is (A) cyanate ester compound 1
It is preferably 4 to 30 parts by weight, more preferably 5 to 30 parts by weight, and 5 to 2 parts by weight with respect to 00 parts by weight.
More preferably, it is 5 parts by weight. If the blending amount of the (B) monohydric phenol compound is less than 4 parts by weight, sufficient dielectric properties cannot be obtained, and the dielectric loss tangent tends to be not sufficiently lowered particularly in the high frequency band. Further, if it exceeds 30 parts by weight, the dielectric loss tangent tends to be rather high, which is not desirable. Therefore, in order to obtain a cured product of a cyanate ester-based resin having a low dielectric loss tangent in the high frequency band provided by the present invention, an appropriate blending amount of (B) monohydric phenol compound with respect to (A) cyanate ester compound is used. Must be compounded.

The (A) cyanate ester compound and the (B) monohydric phenol compound in the present invention are usually used as a modified cyanate ester resin obtained by reacting each of them. That is, it is used as an imide carbonate-modified resin obtained by adding (B) a monohydric phenol compound to (A) cyanate ester compound together with prepolymerization of (A) cyanate ester compound.

When the (A) cyanate ester compound and the (B) monohydric phenol compound are reacted,
(B) The modified cyanate ester resin may be prepared by adding all of the above-mentioned proper blending amount of the monohydric phenol compound from the initial stage of the reaction, and reacting a part of the above-mentioned proper blending amount at the initial stage of the reaction. After cooling, the remaining monohydric phenol compound (B) may be added and reacted at the time of B-stage formation or curing to give a modified cyanate ester resin.

Examples of the (C) polyphenylene ether resin in the present invention include poly (2,6-dimethyl-
Alloyed polymer of 1,4-phenylene) ether, poly (2,6-dimethyl-1,4-phenylene) ether and polystyrene, poly (2,6-dimethyl-1,4-phenylene) ether and styrene-butadiene copolymer Alloyed polymers of, for example, poly (2,6
-Dimethyl-1,4-phenylene) ether and polystyrene alloyed polymer and poly (2,6-dimethyl-
Alloyed polymers of 1,4-phenylene) ether and styrene-butadiene copolymer are preferred. (C) Poly (2,6-dimethyl-in the polyphenylene ether resin
A polymer containing 50% by weight or more of a 1,4-phenylene) ether component is preferable because the cured product has good dielectric properties, and a content of 65% by weight or more is more preferable.

The compounding amount of the (C) polyphenylene ether resin in the present invention is preferably 5 to 300 parts by weight, and more preferably 10 to 200 parts by weight, based on 100 parts by weight of the (A) cyanate ester compound. More preferably, it is more preferably 10 to 100 parts by weight.
If the compounding amount of the (C) polyphenylene ether resin is less than 5 parts by weight, sufficient dielectric properties may not be obtained, and if it exceeds 300 parts by weight, the melt viscosity of the resin becomes high and fluidity becomes insufficient, resulting in moldability. Becomes worse, and (A)
The reactivity of cyanate esters also tends to deteriorate.

Examples of the flame retardant having no reactivity with the (D) cyanate ester compound in the present invention include:
1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclohexane, hexabromocyclododecane, polybromodiphenyl ether,
Examples thereof include brominated polystyrene, brominated polycarbonate, and a brominated triphenyl cyanurate flame retardant represented by the formula (3). Among them, 1,2-dibromo-4
-(1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane,
2,4,6-tris (tribromophenoxy) -1,
A cured product from which 3,5-triazine and the like can be obtained is more preferable because it has good dielectric properties.

[0037]

[Chemical 6]

The amount of the flame retardant having no reactivity with the cyanate ester compound (D) in the present invention is (A).
Total amount of cyanate ester compound, (B) monohydric phenol compound and (C) polyphenylene ether resin 1
It is preferably 5 to 30 parts by weight, more preferably 5 to 20 parts by weight, and 10 to 100 parts by weight.
More preferably, it is 20 parts by weight. If the amount of the flame retardant having no reactivity with the cyanate ester compound (D) is less than 5 parts by weight, the flame resistance tends to be insufficient, and if it exceeds 30 parts by weight, the heat resistance of the resin tends to decrease. There is.

The (E) metal-based reaction catalyst of the present invention is (A)
It accelerates the reaction between the cyanate ester compound and the (B) monohydric phenol compound, and is used as a reaction catalyst when producing a modified cyanate resin composition and as a curing accelerator when producing a laminate. . The metal-based reaction catalysts include manganese, iron, cobalt, nickel, copper,
A metal catalyst such as zinc is used, and specifically, it is used as an organic metal salt compound such as 2-ethylhexanoate or naphthenate and an organic metal complex such as acetylacetone complex. The same metal-based reaction catalyst may be used alone in the reaction accelerator in producing the modified cyanate resin composition and the curing accelerator in producing the laminated plate, or by using two or more different types. Good.

The amount of the (E) metal-based reaction catalyst used in the present invention is preferably 1 to 300 ppm with respect to 1 (g) of the (A) cyanate ester compound, and is 2 to 2 ppm.
It is more preferable to set it to 00 ppm, and 2 to 150 pp
More preferably, it is m. If the compounding amount of the (E) metal-based reaction catalyst is less than 1 ppm, the reactivity and curability tend to be insufficient, and if it exceeds 300 ppm, it becomes difficult to control the reaction, or the curing becomes too fast, resulting in moldability. Tends to get worse. The (E) metal-based reaction catalyst in the present invention may be added at the same time in an amount required as a reaction accelerator and a curing accelerator when a modified cyanate-based resin composition is produced, When producing the modified cyanate-based resin composition, the amount necessary for promoting the modification reaction may be used, and after the completion of the reaction, the remaining catalyst or another metal-based catalyst may be added and mixed as a curing accelerator.

The (F) aromatic hydrocarbon solvent of the present invention is
(C) A solvent that dissolves the polyphenylene ether resin by heating, and a reaction when the (A) cyanate ester compound and the (B) monohydric phenol compound react with each other and (C) the polyphenylene ether resin is compatibilized. It is a solvent. The aromatic hydrocarbon solvent (F) preferably has a boiling point in the range of 70 to 170 ° C., and specific examples thereof include toluene, xylene, ethylbenzene, isopropylbenzene, mesitylene, and the like. The above is used, and toluene is particularly preferable. If the boiling point of the aromatic hydrocarbon solvent (F) is less than 70 ° C., it is likely to volatilize during the coating operation, the viscosity of the varnish increases, and the resin adhesion amount of the prepreg changes, which is not preferable. Further, if the boiling point exceeds 170 ° C., the amount of the solvent remaining in the prepreg tends to increase, which causes voids in the laminated plate and causes deterioration of heat resistance, which is not preferable.

The compounding amount of the (F) aromatic hydrocarbon solvent in the present invention is (C) polyphenylene ether resin 10
It is preferable to use 150 to 500 parts by weight with respect to 0 parts by weight for dissolution by heating, more preferably 150 to 400 parts by weight, still more preferably 150 to 300 parts by weight. The reason why the polyphenylene ether resin is heated and dissolved in the aromatic hydrocarbon solvent is that it is difficult to dissolve when the heating temperature is low,
It is preferable to dissolve at 50 to 140 ° C. because the dissolving time is shortened and the amount of solvent used can be reduced in order to finally produce a high-concentration varnish.

The (G) ketone-based solvent of the present invention reacts the (A) modified cyanate ester-based compound with the (B) monohydric phenol compound in an aromatic hydrocarbon-based solution of the (C) polyphenylene ether resin. It is added to suspend the compatibilizing resin of the modified cyanate ester resin and the polyphenylene ether resin produced in this way, and a poor solvent for the resin is used. The (G) ketone solvent preferably has a boiling point in the range of 50 to 170 ° C.,
Specific examples include acetone, methyl ethyl ketone, 2-
Pentanone, 3-pentanone, methyl isobutyl ketone, 2-hexanone, cyclopentanone, 2-heptanone, cyclohexanone and the like can be mentioned, and one or more kinds of them can be used, and methyl ethyl ketone is particularly preferable. (G) When the boiling point of the ketone solvent is less than 50 ° C.,
It is not preferable because it easily volatilizes during the coating operation, the viscosity of the varnish increases, and the resin adhesion amount of the prepreg changes. Further, if the boiling point exceeds 170 ° C., the amount of the solvent remaining in the prepreg tends to increase, which causes voids in the laminated plate and causes deterioration of heat resistance, which is not preferable.

The amount of the (G) ketone solvent used in the present invention is 5 based on 100 parts by weight of the (F) aromatic hydrocarbon solvent used for dissolving the (C) polyphenylene ether resin.
It is preferable to add 0 to 500 parts by weight and suspend it.
0 to 400 parts by weight is more preferable, and 50 to 300 parts by weight is further preferable.

In the modified cyanate ester resin varnish for a printed wiring board of the present invention, other than the above-mentioned solvent, if necessary, the modified cyanate ester resin and the polyphenylene ether resin may be mixed with each other within a range that does not change the suspension state of the compatibilizing resin. You may use together the solvent of. Specific examples of the solvent that can be used in combination include halogenated hydrocarbons such as trichloroethylene and chlorobenzene, N, N-dimethylformamide, N and N.
Examples thereof include amide-based solvents such as dimethylacetamide and nitrogen-based solvents such as N-methylpyrrolidone. These solvents can be used alone or in combination of two or more.

In the method for producing a modified cyanate ester resin varnish for a printed wiring board of the present invention, (C) polyphenylene ether resin is dissolved by heating in (F) an aromatic hydrocarbon solvent, and then (A) in the solution. A cyanate ester compound and (B) monohydric phenol compound are reacted in the presence of (E) a metal-based reaction catalyst to prepare a compatibilized resin solution of a modified cyanate ester resin and a polyphenylene ether resin, and then a reaction solution It is possible to increase the concentration of the modified cyanate ester resin composition by adding (G) a ketone solvent to the mixture and stirring to suspend the compatibilizing resin, and to react with the (D) cyanate compound. (E) Metal-based reaction by dissolving a flame retardant having no (A) in a reaction liquid of (A) cyanate ester compound and (B) monohydric phenol compound A compatibilized resin solution of the modified cyanate ester resin and the polyphenylene ether resin may be produced in the presence of a medium, or (C) the cyanate ester (A) in an aromatic hydrocarbon-based solution of the polyphenylene ether resin. (D) Cyanate compound after producing a compatibilized resin solution of the modified cyanate ester resin and the polyphenylene ether resin by reacting the compound with the (B) monohydric phenol compound in the presence of the (E) metal-based reaction catalyst A flame retardant having no reactivity with may be added and dissolved.

Further, in the method for producing a modified cyanate ester resin varnish for a printed wiring board of the present invention, (C) a cyanate ester compound and (B) 1 in a polyphenylene ether resin aromatic hydrocarbon solution. In producing a compatibilized resin solution of a modified cyanate ester resin and a polyphenylene ether resin by reacting a hydric phenol compound in the presence of (E) a metal-based reaction catalyst, (B) 1
The whole amount of the hydric phenol compound is used to react with the (A) cyanate ester compound, and then (F)
The compatibilizing resin may be suspended by adding and stirring a ketone solvent, or (C) when reacting with a cyanate ester compound in an aromatic hydrocarbon solution of a polyphenylene ether resin ( B) (A) Cyanate ester compounds are reacted with (E) a metal-based reaction catalyst in the presence of a part of a monohydric phenol compound to obtain a compatible resin solution of a modified cyanate ester resin and a polyphenylene ether resin. After the preparation, the (F) ketone solvent was added to the reaction solution and stirred to suspend the compatibilizing resin, and then (B) 1
The rest of the compounding amount of the hydric phenol compound may be added and dissolved.

Further, in the modified cyanate ester resin varnish for a printed wiring board of the present invention, (C) polyphenylene ether resin is dissolved by heating in (F) an aromatic hydrocarbon solvent, and then (A) cyanate in the solution. After the ester compound and (B) monohydric phenol compound are reacted in the presence of the (E) metal-based reaction catalyst to prepare a compatibilized resin solution of the modified cyanate ester resin and the polyphenylene ether resin, (F) After the ketone-based solvent is charged and stirred to suspend the compatibilizing resin, the same or another type of (E) metal-based reaction catalyst may be further added.

The modified cyanate ester resin varnish for a printed wiring board of the present invention may contain an inorganic filler and other additives, if necessary, in addition to the above essential components.
As the filler, silica, alumina, aluminum hydroxide, calcium carbonate, clay, talc, silicon nitride, boron nitride, titanium oxide, barium titanate, lead titanate,
Strontium titanate or the like can be used. The compounding amount is 250 parts by weight or less with respect to 100 parts by weight of the total amount of the resin composition of the present invention, when a resin varnish of the present invention is impregnated into a substrate such as glass cloth, a uniform resin is obtained. It is preferable in terms of the amount of adhesion and obtaining a good appearance.

The modified cyanate ester resin varnish for a printed wiring board according to the present invention as described above is used, for example, in the production of a prepreg and a laminated board for a printed wiring board as described below. That is, a modified cyanoester ester resin varnish for a printed wiring board of the present invention is impregnated into a base material such as glass cloth and dried to prepare a prepreg for a laminated board. Then, a single or an arbitrary number of the prepregs are stacked and a metal foil is stacked on the upper and lower surfaces or one surface of the prepreg and heat-pressed to form a double-sided or single-sided metal-clad laminate.

[0051]

The present invention will be described in more detail with reference to the following examples. A modified cyanate ester resin varnish for printed wiring boards was manufactured according to the blending amounts shown in Table 1.

(Example 1) A 5 liter 4-neck separable flask equipped with a thermometer, a cooling tube, and a stirrer was used.
(F) 450 g of toluene as the aromatic hydrocarbon solvent and PKN4 as the (C) polyphenylene ether resin
210 g of 752 (trade name, manufactured by Nippon GE Plastics Co., Ltd.) was added, and the mixture was heated to 80 ° C. and dissolved by stirring.
Next, as the (A) cyanate ester compound, 2,2-
Bis (4-cyanatephenyl) propane (Arocy
B-10, product name manufactured by Asahi Ciba Co., Ltd.) 700 g, (B)
62 g of p-tert-octylphenol (manufactured by Wako Pure Chemical Industries, Ltd.) as a monohydric phenol compound
(D) Brominated triphenyl cyanurate as a flame retardant having no reactivity with cyanate ester compounds (Piroguard SR-245, trade name of Daiichi Kogyo Seiyaku Co., Ltd.)
After 135 g was charged and dissolved, (E) 4 g of a 10 wt% toluene solution of cobalt naphthenate (Co content = 8 wt%, manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added as a metal-based reaction catalyst, and reacted at reflux temperature for 1 hour. It was Then cool the reaction mixture,
Methyl ethyl ketone (MEK) when the internal temperature reaches 90 ° C
600 g was added with stirring to suspend. After further cooling to room temperature, 1 g of a 10 wt% toluene solution of zinc naphthenate (Zn content = 8 wt%, manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added and dissolved by stirring to produce a modified cyanate ester resin varnish for printed wiring board ( Solid content concentration = 51% by weight) was produced.

(Example 2) 300 g of toluene and polyphenylene ether resin (PKN4) were placed in a 5-liter 4-neck separable flask equipped with a thermometer, a cooling tube and a stirrer.
752, 140 g of trade name of Japan GE Plastics Co., Ltd.) was added, and the mixture was heated to 80 ° C. and dissolved by stirring.
Next, 2,2-bis (4-cyanatephenyl) propane (ArocyB-10, trade name manufactured by Asahi Ciba Co., Ltd.) 70
0 g, p-tert-octylphenol (manufactured by Wako Pure Chemical Industries, Ltd.) 10 g, and brominated triphenyl cyanurate (Pyroguard SR-245, trade name by Dai-ichi Kogyo Seiyaku Co., Ltd.) 125 g were charged and dissolved, and then manganese naphthenate ( 3 g of a 10% by weight toluene solution of Mn content = 8% by weight, manufactured by Nippon Kagaku Sangyo Co., Ltd. was added and reacted at a reflux temperature for 1 hour. Then, the reaction solution was cooled, and when the internal temperature reached 90 ° C., 600 g of methyl ethyl ketone (MEK) was added with stirring to suspend the reaction solution. After further cooling to room temperature, 73 g of p-tert-octylphenol and 1 g of a 10 wt% toluene solution of zinc naphthenate (Zn content = 8 wt%, manufactured by Nippon Kagaku Sangyo Co., Ltd.) were added and dissolved by stirring to produce a printed wiring board. A modified cyanate ester resin varnish (solid content concentration = 54% by weight) was manufactured.

Example 3 In a 5 liter 4-neck separable flask equipped with a thermometer, a condenser and a stirrer, 300 g of toluene and polyphenylene ether resin (PKN4) were used.
752, product name of Nippon GE Plastics Co., Ltd.) (80 g) was added, and the mixture was heated to 80 ° C. and dissolved by stirring. Next, 800 g of α, α′-bis (4-cyanatophenyl) -m-diisopropylbenzene (RTX-366, a product name of Asahi Ciba Co., Ltd.), and 10 g of p-tert-butylphenol (manufactured by Wako Pure Chemical Industries, Ltd.) 2 g of a 10 wt% toluene solution of iron naphthenate (iron content = 5 wt%, manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added and reacted at a reflux temperature for 1 hour, and then tetrabromocyclooctane (SaytexBC- 48, Albemarle product name)
110 g was added and dissolved. The reaction solution was cooled and the internal temperature was 9
When it reaches 0 ℃, 600g of methyl ethyl ketone (MEK)
Was stirred in and suspended. After further cooling to room temperature, 51 g of p-tert-butylphenol and 2 g of a 10 wt% toluene solution of copper naphthenate (copper content = 5% by weight, manufactured by Nippon Kagaku Sangyo Co., Ltd.) were added and dissolved by stirring to produce a printed wiring board. A modified cyanate ester resin varnish (solid content concentration = 54% by weight) was produced.

Example 4 In a 5 liter 4-neck separable flask equipped with a thermometer, a condenser and a stirrer, 600 g of toluene and polyphenylene ether resin (PKN4) were added.
752, 300 g of Nippon GE Plastics Co., Ltd. product name) was added, and the mixture was heated to 80 ° C. and dissolved by stirring.
Then bis (3,5-dimethyl-4-cyanatophenyl)
600 g of methane (ArocyM-10, trade name of Asahi Ciba Co., Ltd.) and 30 g of p-tert-octylphenol (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and dissolved, and then cobalt naphthenate (Co content = 8 wt%, Nippon Kagaku Co., Ltd.) 4 g of a 10 wt% toluene solution of Sangyo Co., Ltd.) was added and reacted at a reflux temperature for 1 hour, and then hexabromocyclododecane (CD-75P, product name of Great Lakes) 15
0 g was added and dissolved. The reaction liquid is cooled and the internal temperature is 90 ° C.
Then, 750 g of methyl ethyl ketone (MEK) was added with stirring to suspend it. After further cooling to room temperature, 115 g of p-tert-octylphenol was added and dissolved by stirring to produce a modified cyanate ester resin varnish for printed wiring board (solid content concentration = 47% by weight).

(Embodiment 5) In a 5-liter 4-neck separable flask equipped with a thermometer, a cooling tube, and a stirrer, 750 g of toluene and polyphenylene ether resin (PKN4)
752, a product name of Nippon GE Plastics Co., Ltd.) (400 g) was added, and the mixture was heated to 80 ° C. and dissolved by stirring.
Next, 2,2-bis (4-cyanatophenyl) -1,1,
1,3,3,3-hexafluoropropane (Arocy
F-10, trade name of Asahi Chiba Co., Ltd.) 500 g, pt
ert-amylphenol (Wako Pure Chemical Industries, Ltd.)
After adding and dissolving 21 g, 6 g of a 10 wt% toluene solution of copper naphthenate (Cu content = 5 wt%, manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added and reacted at reflux temperature for 1 hour, and then 1,2-dibromo- 150 g of 4- (1,2-dibromoethyl) cyclohexane (Saytex BCL-462, trade name manufactured by Albemarle) was charged and dissolved. Then, the reaction solution was cooled, and when the internal temperature reached 90 ° C., 500 g of methyl ethyl ketone (MEK) was added with stirring to suspend the reaction solution. After cooling to room temperature, 1 g of a 10 wt% toluene solution of manganese naphthenate (Mn content = 8% by weight, manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added and dissolved by stirring to produce a modified cyanate ester resin varnish (solid) for printed wiring boards. Concentration = 46
% By weight).

Comparative Example 1 In Example 1, 1800 g of toluene was added to polyphenylene ether (PKN475).
2, Nippon GE Plastics Co., Ltd. product name) 2
10 g, 2,2-bis (4-cyanatephenyl) propane (ArocyB-10, trade name of Asahi Ciba Co., Ltd.)
700 g and 69 g of 2,2-bis (4-hydroxyphenyl) propane (BPA; bisphenol A, manufactured by Mitsui Toatsu Chemicals, Inc.) were added in place of p-tert-octylphenol, and after stirring and dissolving, cobalt naphthenate (containing Co) was added. Amount of 8% by weight, manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added to 3 g of a 10% by weight toluene diluted solution, and the mixture was reacted at the reflux temperature for 1 hour. Then, as a flame retardant, a brominated bisphenol A type epoxy resin (ESB400, trade name of Sumitomo Chemical Co., Ltd.) having reactivity with a cyanenato group 20
0 g was charged and melted and cooled. However, since the resin solution solidified (grease-like) at around room temperature, 1200 g of toluene was further added and dissolved by stirring to produce a modified cyanate ester resin varnish for a printed wiring board (solid content concentration = 28% by weight).

Comparative Example 2 In Example 1, 1800 g of toluene was mixed with polyphenylene ether resin (PKN47).
52, product name of GE Plastics Co., Ltd.)
210 g, 2,2-bis (4-cyanatephenyl) propane (ArocyB-10, product name manufactured by Asahi Ciba Co., Ltd.) 700 g, and nonylphenol (manufactured by Mitsui Toatsu Chemicals, Inc.) instead of p-tert-octylphenol.
11 g was added, and the mixture was stirred and dissolved, and then cobalt naphthenate (Co
4 g of a 10% by weight diluted solution of toluene having a content of 8% by weight (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added and reacted at a reflux temperature for 1 hour. Then, as a flame retardant, a brominated bisphenol A type epoxy resin (ESB having reactivity with a cyanato group)
400, a product name of Sumitomo Chemical Co., Ltd.) (190 g) was added and melted and cooled. However, since the resin solution solidified (grease-like) at around room temperature, 900 g of toluene was further added and dissolved by stirring to produce a modified cyanate ester resin varnish for a printed wiring board (solid content concentration = 29% by weight).

Comparative Example 3 In Example 1, 1500 g of toluene was added to polyphenylene ether resin (PKN47).
52, product name of GE Plastics Co., Ltd.)
210 g was charged and heated to 80 ° C. to dissolve with stirring, and then 2,2-bis (4-cyanatephenyl) propane (A
rocyB-10, manufactured by Asahi Ciba Co., Ltd.)
An oligomer of 2-bis (4-cyanatephenyl) propane (ArocyB-30, trade name of Asahi Ciba Co., Ltd.) 7
00 g, 67 g of nonylphenol instead of p-tert-octylphenol, and a brominated bisphenol A type epoxy resin (ESB400, trade name manufactured by Sumitomo Chemical Co., Ltd.) having reactivity with a cyanato group as a flame retardant 20
0 g was added and the mixture was heated and dissolved at 80 ° C. for 1 hour. Then, the mixture was cooled to room temperature, 2 g of a 10 wt% toluene solution of zinc naphthenate (Zn content = 8% by weight, manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added, and a modified cyanate ester resin varnish for a printed wiring board (solid content concentration = 44% by weight). However, in this resin varnish, aggregated separation products of the polyphenylene ether resin were observed after 2 days.

Comparative Example 4 In Example 4, 1600 g of toluene and polyphenylene ether resin (PKN47) were used.
52, product name of GE Plastics Co., Ltd.)
300 g, bis (3,5-dimethyl-4-cyanatophenyl) methane (ArocyM-10, product name of Asahi Ciba Co., Ltd.) 600 g, and nonylphenol 9 g instead of p-tert-octylphenol were added, and the mixture was dissolved with stirring. 3 g of a 10 wt% toluene solution of manganese acid (Mn content = 8 wt%, manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added and reacted at a reflux temperature for 1 hour. Then, as a flame retardant, 150 g of tetrabromobisphenol A (Fireguard FG-2000, trade name of Teijin Kasei Co., Ltd.) having reactivity with a cyanato group was charged, dissolved and cooled. However, since the resin solution solidified (grease-like) around room temperature,
1200 g of toluene was further added and dissolved by stirring to produce a modified cyanate ester resin varnish for a printed wiring board (solid content concentration = 27% by weight).

[0061]

[Table 1]

(A) B-10 (trade name of Asahi Chiba Co., Ltd.); 2,
2-bis (4-cyanatophenyl) propane M-10 (trade name, manufactured by Asahi Ciba Co., Ltd.); bis (3,5-dimethyl
-4-Cyanatophenyl) methane F-10 (trade name, manufactured by Asahi Chiba Co., Ltd.); 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane RTX -366 (trade name of Asahi Ciba Co., Ltd.); α, α'-bis (4-cyanatophenyl) -m-diisopropylbenzene B-30 (trade name of Asahi Ciba Co., Ltd.); 2,2-bis (4 -Cyanatophenyl) propane oligomer (B) PBP (manufactured by Wako Pure Chemical Industries, Ltd.); p-tert
-Butylphenol PAP (manufactured by Wako Pure Chemical Industries, Ltd.); p-tert-amylphenol POP (manufactured by Wako Pure Chemical Industries, Ltd.); p-tert-octylphenol BPA (bisphenol A, manufactured by Mitsui Toatsu Chemicals, Inc.);
2,2-bis (4-hydroxyphenyl) propane NP (manufactured by Mitsui Toatsu Chemicals, Inc.); nonylphenol (C) PPO (nonyl PKN4752, a product of Nippon Gee Plastics Co., Ltd.); polyphenylene ether (D) BCL- 462 (product name manufactured by Albemarle); 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane BC-48 (product name manufactured by Albemarle); tetrabromocyclooctane CD-75P (product manufactured by Great Lakes) Hexabromocyclododecane SR-245 (trade name of Dai-ichi Kogyo Seiyaku Co., Ltd.); 2,4,6-
Tris (tribromophenoxy) -1,3,5-triazine ESB-400 (trade name manufactured by Sumitomo Chemical Co., Ltd.); Brominated bisphenol A type epoxy resin TBA (FG-2000, trade name manufactured by Teijin Chemicals Ltd.);
Brominated bisphenol A (E) Co; 10 wt% toluene solution of cobalt naphthenate (Co = 8 wt%, manufactured by Nippon Kagaku Sangyo Co., Ltd.) Zn; Zinc naphthenate (Zn = 8 wt%, manufactured by Nihon Kagaku Sangyo) 10% by weight toluene solution Mn; 10% by weight toluene solution of manganese naphthenate (Mn = 8% by weight, manufactured by Nippon Kagaku Sangyo) Fe; 10% by weight toluene of iron naphthenate (Fe = 5% by weight, manufactured by Nippon Kagaku Sangyo) Solution Cu; 10 wt% toluene solution of copper naphthenate (Cu = 5 wt%, manufactured by Nippon Kagaku Sangyo)

The modified cyanate ester resin varnish for a printed wiring board thus obtained was applied to an E glass cloth having a thickness of 0.2 mm (basis weight: 20).
9 g / m ² ) and heated at 140 ° C. for 5 to 10 minutes (so that the gelling time (170 ° C.) becomes 5 to 7 minutes) and the resin adhesion amount is 40 to 45% by weight. Got In the case of the modified cyanate ester resin varnishes for printed wiring boards of Comparative Examples 1, 2 and 4, since the solid content concentration was low, the above-mentioned impregnation coating operation was repeated twice to laminate a resin adhesion amount of 40 to 45% by weight. A board prepreg was obtained. In the prepreg of Comparative Example 3, separation of cyanate ester resin and polyphenylene ether resin was observed.

Next, four prepregs and 18 μm-thick copper foil were laminated on both sides, press-molded at 170 ° C. and 2.5 MPa for 60 minutes, and then heat-treated at 230 ° C. for 120 minutes to form a copper-clad laminate. It was made. The dielectric properties, solder heat resistance, copper foil peeling strength, and flame resistance of the obtained copper-clad laminate were measured by the following measurement methods. The results are shown in Table 2.
Shown in.

<Characteristic Evaluation Method> -Relative permittivity and dielectric loss tangent / 1 GHz: measured by the triplate structure linear line resonator method. -Solder heat resistance: The test piece from which the copper foil was removed by etching was held in PCT (121 ° C, 0.22 MPa) and then immersed in molten solder at 260 ° C for 20 seconds to examine the appearance. “OK” in the table means that no measling or swelling occurred. -Copper foil peeling strength: Measured according to JIS-C-6481. -Flame resistance: Measured according to the UL-94 vertical test method.

[0066]

[Table 2]

As is clear from Table 2, the laminated boards using the modified cyanate ester resin varnishes for printed wiring boards of Examples 1 to 5 have low relative permittivity and dielectric loss tangent at 1 GHz, Good solder heat resistance and copper foil peeling strength. On the other hand, in the comparative example, the relative dielectric constant and dielectric loss tangent at 1 GHz are high, and the solder heat resistance is poor.

[0068]

The modified cyanate ester resin varnish for printed wiring boards of the present invention has a low dielectric constant and dielectric loss tangent in the high frequency band, good solder heat resistance, adhesiveness and flame resistance, and handles high frequency signals. It is suitable as a resin varnish for printed wiring boards used in the production of printed wiring boards for devices. Further, in the metal-clad laminate obtained by using the resin varnish for a printed wiring board of the present invention, it is possible to increase the concentration of the modified cyanate ester resin, and a device that handles high-frequency signals, for example, a wireless communication-related terminal device or It is suitable for manufacturing printed wiring boards such as antennas and high-speed computers.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C08K 5/03 C08K 5/03 5/13 5/13 5/24 5/24 5/3477 5/3477 C08L 79/00 C08L 79 / 00 Z C09D 7/12 C09D 7/12 171/12 171/12 H05K 1/03 630 H05K 1/03 630B // C07C 261/02 C07C 261/02 C07D 251/34 C07D 251/34 N (C08L 79 / 00 C08L 79/00 71:12) 71:12 (56) Reference JP-A-6-2007096 (JP, A) JP-A-5-311071 (JP, A) JP-A-8-208808 (JP, A) JP-A-8-231847 (JP, A) JP-A-3-275761 (JP, A) JP-A-10-273533 (JP, A) JP-A-64-43527 (JP, A) JP-A-1-158039 (JP, A) JP 63-33506 (JP, B1) JP 4-506826 (JP, A) JP 10-509999 (JP, A) (58 ) investigated the field (Int.Cl. ^7, DB name) C09D 1/00 - 10/00 C09D 101/00 - 201/10 C08G 73/00 - 73/26 C08J 5 / 24 C08K 3/00-13/08 C08L 1/00-101/16 H05K 1/03

Claims (17)

(57) [Claims] 1. A cyanate ester compound represented by formula (A), a monohydric phenol compound represented by formula (B), and a polyphenylene ether resin (C).
For a printed wiring board containing (D) a flame retardant having no reactivity with a cyanate ester compound, (E) a metal reaction catalyst, (F) an aromatic hydrocarbon solvent and (G) a ketone solvent as essential components. Modified cyanate ester resin varnish. [Chemical 1] [Chemical 2] 2. A modified cyanate ester resin varnish for a printed wiring board, comprising 10 parts of (A) cyanate ester compound.
4 parts of (B) monohydric phenol compound is added to 0 part by weight.
A modified cyanate ester resin varnish for a printed wiring board, characterized by being mixed in an amount of ˜30 parts by weight. 3. A resin varnish for printed wiring boards, a modified cyanate ester resin obtained by reacting (A) a cyanate ester compound with (B) a part or all of a monohydric phenol compound, and (C) polyphenylene. Ether resin,
(D) a flame retardant having no reactivity with a cyanate ester compound, (E) a metal-based reaction catalyst, (F) an aromatic hydrocarbon-based solvent, and (G) a ketone-based solvent are contained as essential components. The modified cyanate ester resin varnish for a printed wiring board according to claim 1 or 2. 4. The (A) cyanate ester compound is
4. Any one of 2,2-bis (4-cyanatophenyl) propane and bis (3,5-dimethyl-4-cyanatophenyl) methane or a mixture of both, any one of claims 1 to 3. The modified cyanate ester resin varnish for a printed wiring board according to [1]. 5. The (B) monohydric phenol compound is p-
The modified cyanate ester resin varnish for a printed wiring board according to any one of claims 1 to 4, which is at least one kind selected from tert-butylphenol, p-tert-amylphenol, and p-tert-octylphenol. 6. The (C) polyphenylene ether resin comprises:
An alloyed polymer of poly (2,6-dimethyl-1,4-phenylene) ether and polystyrene or styrene-butadiene copolymer, wherein poly (2,6-dimethyl-
The modified cyanate ester resin varnish for a printed wiring board according to claim 1, which contains 50% by weight or more of 1,4-phenylene) ether. 7. A flame retardant having no reactivity with the (D) cyanate ester compound is 1,2-dibromo-4-
7. One of alicyclic flame retardants selected from (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane and hexabromocyclododecane, or a mixture of two or more thereof. The modified cyanate ester resin varnish for a printed wiring board according to [1]. 8. A flame retardant having no reactivity with the (D) cyanate ester compound is a brominated triphenyl cyanurate flame retardant represented by the formula (3) or at least one of these and other cyanate esters. The modified cyanate ester resin varnish for a printed wiring board according to any one of claims 1 to 6, which is a mixture of two or more kinds of a compound and a flame retardant having no reactivity. [Chemical 3] 9. (E) The metal-based reaction catalyst is manganese, iron,
9. One or more selected from 2-ethylhexanoate, naphthenate and acetylacetone complex of cobalt, nickel, copper and zinc.
A modified cyanate ester resin varnish for printed wiring boards according to any one of 1. 10. (F) an aromatic hydrocarbon solvent (C)
15 to 100 parts by weight of polyphenylene ether resin
The modified cyanate ester resin varnish for a printed wiring board according to any one of claims 1 to 9, which is heated and dissolved in an amount of 0 to 500 parts by weight. 11. The method according to claim 1, wherein the ketone solvent (G) is used in an amount of 50 to 500 parts by weight with respect to 100 parts by weight of the aromatic hydrocarbon solvent (F). Modified cyanate ester resin varnish for printed wiring boards. 12. The modified cyanate ester resin varnish for a printed wiring board according to claim 1, wherein the boiling point of (F) the aromatic hydrocarbon solvent is 70 to 170 ° C. 13. The printed wiring according to claim 1, wherein (F) the aromatic hydrocarbon solvent is at least one selected from the group consisting of toluene, xylene, ethylbenzene, isopropylbenzene and mesitylene. Modified cyanate ester resin varnish for boards. 14. The boiling point of (G) a ketone-based solvent is 50 to 1
The modified cyanate ester resin varnish for a printed wiring board according to any one of claims 1 to 13, which has a temperature of 70 ° C. 15. The (G) ketone solvent is any one or more of acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, methyl isobutyl ketone, 2-hexanone, cyclopentanone, 2-heptanone or cyclohexanone. The modified cyanate ester resin varnish for a printed wiring board according to any one of claims 1 to 14. 16. A laminated board, comprising: impregnating a base material with the modified cyanate ester resin varnish for a printed wiring board according to claim 1 and then drying the varnish at 80 to 200 ° C. Manufacturing method of prepreg. 17. A metal-clad laminate, comprising one or a plurality of laminate prepregs according to claim 16 and a metal foil laminated on the upper and lower surfaces or one surface thereof and heated under pressure. Method.