JP2003332701A - Modified cyanate ester resin varnish for printed wiring board, prepreg for laminate using same, and method for manufacturing metal-clad laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modified cyanate ester resin varnish having good thermal resistance which exerts formability and processability similar to those of a conventional thermosetting resin laminate and provides a printed wiring board of a sufficiently low-loss property with a low dielectric dissipation factor in a high frequency band, and provide prepreg for a laminate using the varnish, and a method for manufacturing a metal-clad laminate. <P>SOLUTION: The resin varnish for a printed wiring board comprises a modified cyanate ester base resin which comprises, as essential components, (A) a cyanate ester compound, (B) a monovalent phenolic compound, (C) a polypropylene resin, (D) a flame retardant which is nonreactive with a cyanate ester compound, (E) a metal base reaction catalyst, (F) an aromatic hydrocarbon base solvent and (G) a ketone base solvent. This varnish is impregnated into a base, followed by drying for producing prepreg for the laminate. A certain number of prepreg sheets and metal foils are stacked, pressurized and heated to obtain the metal-clad laminate. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printed wiring board used for a high-speed computer or the like in which a terminal loss is required for low loss in a high frequency band related to wireless communication, an antenna, and a microprocessor whose operating frequency exceeds 1 GHz. The present invention relates to a resin composition and a resin varnish suitable for producing the substrate. That is, the present invention relates to a resin varnish for printed wiring boards using a modified cyanate ester-based curable resin composition having excellent high-frequency characteristics, and a method for producing a prepreg for laminates and a metal-clad laminate using the resin varnish. More specifically, it has good heat resistance, exhibits moldability and processability similar to conventional thermosetting resin laminates such as epoxy resin, and has low dielectric loss, low dielectric loss tangent especially in high frequency band. The present invention relates to a resin varnish for printed wiring boards using a curable resin composition capable of producing an excellent high-density multilayer wiring board, a prepreg for laminated boards and a method for producing a metal-clad laminated board using the resin varnish.

[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 devices related to mobile communication that handle 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 5 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 whose operating frequency exceeds 1 GHz and a high frequency signal are being developed. 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. Further, as a material for improving high frequency characteristics by using a thermoplastic resin, a resin composition of polyphenylene ether (PPO or PPE) and a crosslinkable polymer / monomer disclosed in JP-B-5-77705 and JP-B-6- A polyphenylene ether resin composition having good dielectric properties among heat resistant thermoplastic resins such as a resin composition of a polyphenylene ether having a specific curable functional group and a crosslinkable monomer disclosed in Japanese Patent No. 92533. There is a method of using.

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

[0007]

[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 Fair 5-777
Although the method disclosed in Japanese Patent Publication No. 05 and Japanese Patent Publication No. 6-92533 improves the dielectric properties, it has a high melt viscosity and a high fluidity because the resin composition is mainly composed of polyphenylene ether, which is originally a thermoplastic polymer. There was a problem of shortage. 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.

Japanese Examined Patent Publication No. 63-33506 and Japanese Unexamined Patent Publication No. 5-
In the method disclosed in Japanese Patent No. 311071, since the thermosetting resin used in combination with the polyphenylene ether 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 still. There was a problem that it was insufficient. Incidentally, when the amount of polyphenylene ether compounded is increased to improve the high-frequency characteristics, the melt viscosity of the resin composition becomes high and the flowability becomes insufficient, resulting in poor moldability, as in the case of the aforementioned polyphenylene ether resin composition. There was a point.

Further, the resin composition obtained by kneading polyphenylene ether as disclosed in Japanese Patent Publication No. 61-18937 has good dielectric properties, and when modified with a cyanate ester resin, the melt viscosity becomes low, so that the resin composition is molded. However, when the cyanate ester alone is used as the curable component, the dielectric properties of the resin cured product tend to have a high dielectric loss tangent relative to the value of the permittivity, which reduces transmission loss in the high frequency band. There was a problem that it could not be reduced sufficiently. Further, when the amount of cyanate ester is reduced (the amount of polyphenylene ether is increased) to lower the dielectric loss tangent, the melt viscosity of the resin composition is increased and the fluidity is insufficient as in the case of the polyphenylene ether resin composition described above. Therefore, there is a problem that the moldability is poor. In view of such circumstances, a method (Japanese Patent Application No. 9-80033) has been proposed in which a composition obtained by modifying a specific cyanate ester resin with a monohydric phenol compound is used as a part or all of the matrix resin. Although it was possible to obtain a resin composition having good high frequency characteristics by modifying a specific cyanate ester resin with a monohydric phenol compound, it is not possible to cope with further higher frequency that is expected to progress in the future. There was a problem that it was enough.

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, particularly dielectric loss tangent in a high frequency band. Provided are a resin varnish for a printed wiring board of a curable resin composition capable of producing a high-density multilayer wiring board excellent in low loss property, and a method for producing a prepreg for a laminated board and a metal-clad laminated board using the same. .

[0011]

The present invention relates to the following: (1) (A) Cyanate ester compound represented by the formula [1]

[0012]

[Chemical 4]

[0013]

[Chemical 5]

(In the formula, R ₄ and R ₅ represent a hydrogen atom or a lower alkyl group, and may be the same or different, and n is a positive integer of 1 to 2), (C ) Polypropylene resin (D) Modified cyanate ester containing flame retardant (E) metal-based reaction catalyst (F) aromatic hydrocarbon-based solvent and (G) ketone-based solvent that are not reactive with cyanate ester compounds as essential components Resin-based resin varnish for printed wiring boards.

(2) A resin varnish for a printed wiring board, characterized in that 4 to 30 parts by weight of the monohydric phenol compound (B) is blended with 100 parts by weight of the cyanate ester compound (A).

(3) A modified cyanate ester resin obtained by reacting (A) a cyanate ester compound with (B) a part or all of a monohydric phenol compound,
(C) polypropylene resin, (D) flame retardant having no reactivity with cyanate ester compounds, (E) metal reaction catalyst, (F) aromatic hydrocarbon solvent and (G) ketone solvent as essential components The resin varnish for a printed wiring board according to the above (1) or (2), characterized by containing.

(4) The (A) cyanate ester compound is either 2,2-bis (4-cyanatophenyl) propane or 2,2-bis (3,5-dimethyl-4-cyanatophenyl) methane. The resin varnish for printed wiring boards according to the above (1) to (3), which is one kind or a mixture thereof.

(5) The resin varnish for a printed wiring board according to the above (1) to (4), wherein the (B) monohydric phenol compound is p- (α-cumyl) phenol.

(6) The flame retardant having no reactivity with the (D) cyanate ester compound is 1,2-dibromo-4.
The alicyclic flame retardant selected from-(1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane and hexabromocyclododecane, or a mixture of two or more of these (1) to (5). Resin varnish for printed wiring boards. (7) The flame retardant having no reactivity with the (D) cyanate ester compound is represented by the formula [3]

[0020]

[Chemical 6] (In the formula, l, m, and n represent integers of 1 to 5, and may be the same or different, respectively) or a brominated triphenylcyanurate flame retardant or at least one or more thereof. The resin varnish for a printed wiring board according to (1) to (6) above, which is a mixture of two or more kinds of a flame retardant having no reactivity with other cyanate ester compounds.

(8) (E) The metal-based reaction catalyst is one or more selected from manganese, iron, cobalt, nickel, copper, zinc 2-ethylhexanoate, naphthenate, and acetylacetone complex. A resin varnish for a printed wiring board according to any one of (1) to (7) above.

(9) 150 parts of (F) aromatic hydrocarbon solvent per 100 parts by weight of (C) polypropylene resin.
The resin varnish for a modified printed wiring board according to the above (1) to (8), wherein the resin varnish is heated to dissolve by using about 500 parts by weight.

(10) 100 to 50 parts of the (G) ketone solvent to 100 parts by weight of the (F) aromatic hydrocarbon solvent.
The resin varnish for a printed wiring board according to any one of (1) to (9) above, which is used in parts by weight.

(11) The resin varnish for a printed wiring board according to the above (1) to (10), wherein the boiling point of the aromatic hydrocarbon solvent (F) is 70 to 170 ° C.

(12) (F) For a printed wiring board according to the above (1) to (11), wherein the aromatic hydrocarbon solvent is at least one selected from the group consisting of toluene, xylene, ethylbenzene, isopropylbenzene and mesitylene. Resin varnish.

(13) The boiling point of the ketone solvent (G) is 5
The resin varnish for a printed wiring board according to (1) to (12), which has a temperature of 0 to 170 ° C.

(14) (G) The ketone solvent is at least one selected from the group consisting of acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, methyl isobutyl ketone, 2-hexanone, cyclopentanone, 2-heptanone and cyclohexanone. (1) to (1
3) The resin varnish for printed wiring boards according to 3).

(15) A prepreg for laminated boards, characterized in that the substrate is impregnated with the resin varnish for printed wiring board according to any one of the above (1) to (14) and then dried at 80 to 200 ° C. Manufacturing method

(16) A method for producing a metal-clad laminate, which comprises laminating an arbitrary number of prepregs for laminates according to the above (15), further laminating a metal foil on one side or both sides and heating under pressure.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention comprises (A) a cyanate ester compound represented by the formula [1], (B) a monohydric phenol compound represented by the formula [2], (C) a polypropylene resin, and (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 modified cyanate ester-based resin containing (K) a ketone-based solvent as essential components. A method for producing a resin varnish for a printed wiring board, a prepreg for a laminate and a metal-clad laminate using the resin varnish. In addition to the above, the present invention is
(A) 4 to 30 parts by weight of the monohydric phenol compound represented by the formula (2) is blended with 100 parts by weight of the cyanate ester compound represented by the formula [1]. A method for producing a resin varnish for a printed wiring board of a modified cyanate ester resin, which has a low dielectric loss tangent in a band and is excellent in low loss property, a prepreg for a laminate and a metal-clad laminate using the resin varnish.

Dielectric properties such as polymer materials are greatly affected by the orientation polarization of dipoles, and therefore the dielectric constant can be lowered by reducing the polar groups in the molecule, and the dielectric loss tangent can be reduced by suppressing the mobility of the polar groups. 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 not possible that all the cyanato groups in the cyanate ester resin react to form a triazine structure, and the reaction system becomes fluid as the curing reaction progresses. 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 according to the present invention, by mixing (B) a monohydric phenol compound in an appropriate amount, the unreacted cyanato group is converted into an imide carbonate to reduce its polarity. It is an object to reduce the dielectric constant and dielectric loss tangent of a cured product. The material used for this purpose has high reactivity with cyanato groups,
In addition, it is monofunctional, has a relatively low molecular weight, and has good compatibility with cyanate ester resins (there are similar molecular structures).
The compound is considered suitable. The monohydric phenol compound used in the resin composition of the present invention is a compound specified for such reasons.

Conventionally, as a cocatalyst for the trimerization reaction of cyanate ester (formation of triazine ring), phenol compounds such as nonylphenol are 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 examining the compounding amount of the phenolic compound by the present inventors, it was confirmed that the compounding amount of the phenolic compound in a larger amount than in the conventional case lowers 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 resin varnish for printed wiring board of the present invention, the thermoplastic resin (C) having a good dielectric property is blended with the above-mentioned modified cyanate ester resin to improve the dielectric property. . The cyanate ester resin and the polypropylene 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 the monohydric phenol compound is carried out in a solvent solution of polypropylene resin,
It was found that a so-called "semi-IPN" resin was produced and a uniform resin solution was obtained.

That is, in the resin varnish for printed wiring board of the present invention, (C) polypropylene resin is heated and dissolved using (F) aromatic hydrocarbon solvent, and (A) cyanate ester compound is dissolved in the solution. And oligomerization of (A) cyanate ester compound and (B) monohydric phenol compound are carried out to produce a compatibilizing resin of modified cyanate ester resin and polypropylene resin. Regarding compatibilization at this time, it is unlikely that the modified cyanate ester resin and the polypropylene resin form a chemical bond, and instead, a part of the modified cyanate ester resin is entangled in the molecular chain of the polypropylene resin and the oligomer It is considered that the so-called “semi-IPN” resin is being produced due to the progress of chemical conversion. In this case, in order to promote the entanglement of the molecular chain, the molecular chain of the polypropylene resin being dissolved is widened, and a part of the modified cyanate ester resin is easily entangled in the molecular chain of the polypropylene resin. At the same time, it is preferable to use (F) an aromatic hydrocarbon solvent, which also dissolves the modified cyanate ester resin well, 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 composition of the present invention also has a high viscosity in the state of (F) aromatic hydrocarbon-based solution. It becomes close to solid in a very high concentration solution. 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, in order to obtain a high-concentration resin varnish for a printed wiring board, the present inventors used a compatibilizing resin solution of a modified cyanate ester resin and a polypropylene resin produced in an aromatic hydrocarbon-based solution. , (G) a ketone-based solvent is added, stirred and suspended to reduce the viscosity, and (F) an aromatic hydrocarbon-based solvent that is a compatibilizing resin of a high concentration modified cyanate ester resin and a polypropylene resin. A resin for a printed wiring board, which is capable of producing a prepreg having a relatively high concentration and a high resin adhesion amount, by preparing (G) a ketone solvent and suspending it after the solution is prepared. I devised a varnish.

The flame retardant used in the resin varnish for a printed wiring board of the present invention is reactive with a cyanate ester compound so as not to inhibit the reaction between the (A) cyanate ester compound and the (B) monohydric phenol compound. It is essential not to have, and since it is a hydrocarbon low-polarity compound, the dielectric properties of the cured product are less likely to deteriorate. 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.

The resin varnish for printed wiring boards and the method for producing the same according to the present invention include (A) a cyanate ester compound represented by the formula [1], (B) a monohydric phenol compound represented by the formula [2], ( In a method for producing a resin varnish for a printed wiring board, which comprises C) a polypropylene resin, (D) a flame retardant having no reactivity with a cyanate ester compound, and (E) a metal-based reaction catalyst as essential components, a modified cyanate ester-based resin, (C) Polypropylene resin is heated and dissolved in (F) aromatic hydrocarbon solvent, and then (A) cyanate ester compound and (B) monohydric phenol compound are added to (E) metal reaction catalyst in the solution. After reacting in the presence of a modified cyanate ester resin and a polypropylene resin to prepare a compatibilizing resin solution, (G) a ketone-based solvent is added to the reaction solution and agitated to obtain a compatible solution. And characterized by suspending the resin, a high concentration capable printed wiring board resin varnish and a method of manufacturing modified cyanate ester resin composition having excellent high-frequency characteristics.

The cyanate ester compound (A) in the present invention is a cyanate ester compound having two cyanato groups in one molecule as shown in the formula [1].
Examples of the compound represented by the formula [1] include bis (4
-Cyanatophenyl) ethane, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (3,5-dimethyl-4-cyanatophenyl) methane, 2,2-bis (4-si) Anatophenyl) -1,1,1,3,3,3-
Hexafluoropropane, α, α′-bis (4-cyanatophenyl) -m-diisopropylbenzene, cyanate esterification products of phenol-added dicyclopentadiene polymer, and the like can be mentioned. Among them, 2,2-bis (4
-Cyanatophenyl) propane and 2,2-bis (3,3
5-dimethyl-4-cyanatophenyl) 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 a monohydric phenol represented by the formula [2],
A compound having good heat resistance is preferable. Examples of the compound represented by the formula [2] include p- (α-cumyl) phenol. The monohydric phenol compound (B) may be used alone or in combination of two or more.

In the present invention, the compounding amount of the (B) monohydric phenol compound 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.
It is particularly preferable to use 5 parts by weight. If the blending amount of the monohydric phenol compound (B) 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, (B) a monohydric phenol compound is added in an appropriate amount relative to (A) a cyanate ester compound. 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 other. 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 compounding amounts of the monohydric phenol compounds from the initial stage of the reaction and reacting them, or by reacting a part of the above-mentioned proper compounding amounts 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 obtain a modified cyanate ester resin. The polypropylene resin (C) in the present invention preferably has a weight average molecular weight of 10 ³ to 10 ⁷ , more preferably 10 ⁴ to 10 ⁶ .

Further, a copolymer with butadiene, maleic anhydride or the like can be used, and it is effective in improving the compatibility and heat resistance. The compounding amount of the (C) polypropylene resin in the present invention is (A) cyanate ester compound 1
The amount is preferably 5 to 300 parts by weight, more preferably 10 to 200 parts by weight,
It is particularly preferable that the amount is 10 to 100 parts by weight. (C)
If the blending amount of the polypropylene 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 the fluidity becomes insufficient, resulting in poor moldability. Further, the reactivity of the (A) cyanate ester 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 polypropylene, brominated polycarbonate, and a brominated triphenyl cyanerate 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,
More preferred is 3,5-triazine. The blending amount of the flame retardant having no reactivity with the (D) cyanate ester compound in the present invention is 100 parts by weight in total of the (A) cyanate ester compound, the (B) monohydric phenol compound and the (C) polypropylene resin. 5 to 30 parts by weight is preferable, 5 to 20 parts by weight is more preferable, and 10 to 20 parts by weight is particularly preferable. 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 promotes the reaction between the cyanate ester compound and the monohydric phenol compound (B), and is used as a reaction catalyst when producing a modified cyanate resin composition and a curing accelerator when producing a laminated board. . 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 1 with respect to the (A) cyanate ester compound.
-300 ppm is preferable, and 2-200 pp
It is more preferably m, and particularly preferably 2 to 150 ppm. 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 for heating and dissolving polypropylene resin,
Further, it serves as a reaction solvent when the reaction of the cyanate ester compound (A) and the monohydric phenol compound (B) and the compatibilization of the polyphenylene ether (C) are carried out.
(F) The aromatic hydrocarbon solvent has a boiling point of 70 to 17
It is preferably in the range of 0 ° C., and specific examples thereof include toluene, xylene, ethylbenzene, isopropylbenzene, mesitylene, and the like. One or more of these are 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 blending amount of the (F) aromatic hydrocarbon solvent in the present invention is preferably 150 to 500 parts by weight with respect to 100 parts by weight of the (C) polypropylene resin to dissolve by heating, and 150 to 400 parts by weight. Is more preferable, and 15
0 to 300 parts by weight is particularly preferred. The (G) ketone solvent of the present invention was produced by reacting (A) modified cyanate ester compounds with (B) monohydric phenol compound in an aromatic hydrocarbon solution of (C) polypropylene resin. It is added to suspend the compatibilizing resin of modified cyanate ester resin and polypropylene resin,
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., and specific examples thereof include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, methyl isobutyl ketone, 2-hexanone, cyclopenta. Non-, 2-heptanone, cyclohexanone, etc. are mentioned, One or more types are used among these, Methyl ethyl ketone is especially preferable. If the boiling point of the (G) 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 blending amount of the (G) ketone-based solvent in the present invention is the amount used in the dissolution of the (C) polypropylene resin (F).
50 to 50 with respect to 100 parts by weight of the aromatic hydrocarbon solvent
It is preferable to add 0 part by weight to make the suspension 50 to 40
0 parts by weight is more preferable, and 50 to 300 parts by weight is particularly preferable. In the resin varnish for a printed wiring board of the present invention, if necessary, in addition to the above solvent, other solvents may be used in combination within a range that does not change the suspension state of the compatibilizing resin of the modified cyanate ester resin and the polypropylene resin. good. Specific examples of the solvent that can be used in combination include halogenated hydrocarbons such as trichloroethylene and chlorobenzene, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and nitrogen solvents such as N-methylpyrrolidone. These solvents can be used alone or in combination of two or more.

In the method for producing a resin varnish for a printed wiring board of the present invention, (C) polypropylene resin is dissolved by heating in (F) an aromatic hydrocarbon solvent, and then (A) cyanate ester compound is dissolved in the solution. And (B) a monohydric phenol compound are reacted in the presence of (E) a metal-based reaction catalyst to produce a compatibilized resin solution of a modified cyanate ester resin and a polypropylene resin, and then (G) a ketone is added to the reaction solution. A flame retardant which is capable of increasing the concentration of the modified cyanate ester resin composition by suspending the compatibilizing resin by introducing a system solvent and stirring it, and which has no reactivity with the (D) cyanate compound Is dissolved in a reaction solution of (A) a cyanate ester compound and (B) a monohydric phenol compound, and (E) a modified cyanate ester resin and polyp A compatibilized resin solution with a pyrene resin may be produced, or (C) a cyanate ester compound and (B) a monohydric phenol compound in an aromatic hydrocarbon solution of a polypropylene resin ( E) After reacting in the presence of a metal-based reaction catalyst to prepare a compatibilized resin solution of a modified cyanate ester resin and a polypropylene resin, (D) a cyanate compound and a flame retardant having no reactivity are added and dissolved. Is also good.

Further, in the method for producing a resin varnish for a printed wiring board according to the present invention, (C) a cyanate ester compound and (B) a monohydric phenol compound in an aromatic hydrocarbon solution of polypropylene resin. When (E) is reacted in the presence of a metal-based reaction catalyst to produce a compatibilized resin solution of a modified cyanate ester resin and a polypropylene resin, all of the compounding amount of the (B) monohydric phenol compound is used. (A) by reacting with a cyanate ester compound,
Thereafter, the compatibilizing resin may be suspended by adding (F) a ketone-based solvent and stirring, or may be reacted with (C) a cyanate ester compound in an aromatic hydrocarbon-based solution of (C) polypropylene resin. Occasionally, a part of the (B) monohydric phenol compound is used to react with the (A) cyanate ester compound in the presence of the (E) metal-based reaction catalyst to obtain a compatible resin of the modified cyanate ester resin and the polypropylene resin. A solution is prepared, and the reaction solution is charged with (F) a ketone solvent to stir the compatibilizing resin, and then the remaining (B) monohydric phenol compound is added and dissolved. Is also good.

Further, in the method for producing a resin varnish for a printed wiring board according to the present invention, (C) polypropylene resin is heated and dissolved in (F) aromatic hydrocarbon solvent, and then (A) cyanate ester is dissolved in the solution. Compound (B) monohydric phenol compound is reacted in the presence of (E) metal-based reaction catalyst to prepare a compatibilized resin solution of modified cyanate ester resin and polypropylene resin, and then (F) ketone-based compound After pouring into the solvent and stirring to suspend the compatibilizing resin,
Further, the same or another type of (E) metal-based reaction catalyst may be blended.

The 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-mentioned 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 and the like can be used. The compounding amount is 200 with respect to 100 parts by weight of the total amount of the resin composition of the present invention.
It is preferable that the amount is less than or equal to parts by weight.

The prepreg for a laminated board in the present invention is produced by impregnating a fiber substrate with a resin varnish for a printed wiring board and then drying. The material and thickness of the fiber base material are not particularly limited, but it is preferable to use a glass cloth of 0.03 to 0.2 mm. The drying temperature is preferably 80 to 200 ° C, more preferably 120 to 180 ° C. The amount of resin adhered to the fiber base material is preferably 35 to 70%, more preferably 40 to 60%, based on the total amount of the resin solid content and the fiber base material.

The metal-clad laminate of the present invention is produced by stacking an arbitrary number of laminate prepregs, further stacking a metal foil on one side or both sides thereof, and heating under pressure. Copper foil, aluminum foil, or the like is used as the metal foil, and a foil having a thickness of 3 to 105 μm is preferably used. As pressurizing and heating conditions, it is preferable to perform press molding for 0.5 to 3.0 hours at a heating temperature of 150 to 230 ° C. and a pressure of 2 to 5 MPa. If necessary, heat treatment may be further added.

[0059]

The present invention will be described in more detail with reference to the following examples. Resin varnishes for printed wiring boards were manufactured according to the blending amounts shown in Table 1. Example 1 To a 5-liter four-necked separable flask equipped with a thermometer, a cooling tube, and a stirrer, 450 g of toluene and 210 g of polypropylene resin (manufactured by Wako Pure Chemical Industries, Ltd.) were charged, and the temperature was 80 ° C.
It was heated to and dissolved by stirring. Next, 700 g of 2,2-bis (4-cyanatephenyl) propane (ArocyB-10, manufactured by Asahi Ciba), 64 g of p- (α-cumyl) phenol (manufactured by San Technochemical), brominated triphenylcyanurate (Pyroguard SR-). 245, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 13
After charging and dissolving 5 g, cobalt naphthenate (Co content =
4% of a 10% toluene solution of 8%, 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, methyl ethyl ketone (ME
600 g of K) was added with stirring to suspend it. After further cooling to room temperature, zinc naphthenate (Zn content =
A resin varnish for a printed wiring board (solid content concentration = 51%) was manufactured by adding 1 g of a 10% toluene solution of 8%, manufactured by Nippon Kagaku Sangyo Co., Ltd. and stirring and dissolving.

Example 2 300 g of toluene and 140 g of polypropylene resin (manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a 5-liter four-necked separable flask equipped with a thermometer, a cooling tube, and a stirrer, and the temperature was 80 ° C.
It was heated to and dissolved by stirring. Next, 700 g of 2,2-bis (4-cyanatephenyl) propane (ArocyB-10, manufactured by Asahi Ciba), 10 g of p- (α-cumyl) phenol (manufactured by San Technochemical), brominated triphenylcyanurate (Pyroguard SR-). 245, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 12
After 5 g was charged and dissolved, manganese naphthenate (Mn content =
3% of a 10% toluene solution of 8%, 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, methyl ethyl ketone (ME
600 g of K) was added with stirring to suspend it. After further cooling to room temperature, 75 g of p- (α-cumyl) phenol and 1 g of a 10% toluene solution of zinc naphthenate (Zn content = 8%, manufactured by Nippon Kagaku Sangyo Co., Ltd.) were added and dissolved by stirring to produce a printed wiring board. A resin varnish (solid content concentration = 54%) was produced.

Example 3 300 g of toluene and 80 g of polypropylene resin (manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a 5 liter 4-neck separable flask equipped with a thermometer, a cooling tube and a stirrer, and heated to 80 ° C. It was dissolved with stirring. Next, α, α'-bis (4-cyanatophenyl) -m-diisopropylbenzene (RTX-
366, manufactured by Asahi Ciba) 800 g, p- (α-cumyl) phenol (manufactured by San Techno Chemical) 10 g, and dissolved.
1 of iron naphthenate (iron content = 5%, made by Nippon Kagaku Sangyo)
2 g of 0% toluene solution was added and reacted at reflux temperature for 1 hour, and then 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane (Saytex BCL-46).
2, Albemarle) (110 g) was added and dissolved. The reaction liquid was cooled, and when the internal temperature reached 90 ° C., 600 g of methyl ethyl ketone (MEK) was added with stirring to suspend it. After further cooling to room temperature, 75 g of p- (α-cumyl) phenol and 2 g of 10% toluene solution of copper naphthenate (copper content = 5%, manufactured by Nippon Kagaku Sangyo Co., Ltd.) were added and dissolved by stirring to produce a printed wiring board. Resin varnish (solid concentration = 54%)
Was manufactured.

Example 4 600 g of toluene and 300 g of polypropylene resin (manufactured by Wako Pure Chemical Industries) were placed in a 5-liter four-necked separable flask equipped with a thermometer, a cooling tube, and a stirrer, and the temperature was 80 ° C.
It was heated to and dissolved by stirring. Then bis (3,5-dimethyl-
4-cyanatophenyl) methane (ArocyM-10,
600 g of Asahi Ciba) and 30 g of p- (α-cumyl) phenol (manufactured by San Techno Chemical) were added and dissolved, and then 4 g of a 10% toluene solution of cobalt naphthenate (Co content = 8%, manufactured by Nippon Kagaku Sangyo) was added. The mixture was reacted at reflux temperature for 1 hour, and then hexabromocyclododecane (CD-75
150 g (P, product of Great Lakes) was added and dissolved.
The reaction solution was cooled, and when the internal temperature reached 90 ° C., 750 g of methyl ethyl ketone (MEK) was added with stirring to suspend the reaction solution. After further cooling to room temperature, 120 g of p- (α-cumyl) phenol was added and dissolved by stirring to produce a resin varnish for printed wiring board (solid content concentration = 47%).

Example 5 To a 5-liter four-necked separable flask equipped with a thermometer, a cooling tube, and a stirrer, 750 g of toluene and 400 g of polypropylene resin (manufactured by Wako Pure Chemical Industries, Ltd.) were charged, and the temperature was 80 ° C.
It was heated to and dissolved by stirring. Next, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane (ArocyF-10, manufactured by Asahi Ciba) 500
g, 28 g of p- (α-cumyl) phenol (manufactured by San Techno Chemical) was added and dissolved, and then 6 g of a 10% toluene solution of copper naphthenate (Cu content = 5%, manufactured by Nippon Kagaku Sangyo) was added and the mixture was refluxed at 1 After reacting for a time, 150 g of tetrabromocyclooctane (Saytex BC-48, manufactured by Albemarle) was charged and dissolved. Then, the reaction solution was cooled, and when the internal temperature reached 90 ° C, methyl ethyl ketone (ME
K) 500 g was added with stirring to suspend. After cooling to room temperature, manganese naphthenate (Mn content = 8
%, Manufactured by Nippon Kagaku Sangyo Co., Ltd., 1 g of 10% toluene solution was added, and dissolved by stirring to produce a resin varnish for printed wiring board (solid content concentration =
46%).

Comparative Example 1 In Example 1, 210 g of polypropylene resin (manufactured by Wako Pure Chemical Industries) and 1800 g of toluene, 2,2-bis (4
-Cyanatephenyl) propane (Arocy B-1
0, Asahi Ciba) 700 g and 2,2-bis (4-hydroxyphenyl) propane (BPA; bisphenol A, Mitsui Chemicals) 69 g in place of p- (α-cumyl) phenol, and after stirring and dissolving, naphthene 3 g of a 10% toluene diluted solution of cobalt acid (Co content = 8%, manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added, and the mixture was reacted at the reflux temperature for 1 hour. Then, as a flame retardant, a brominated bisphenol A type epoxy resin (ESB40 having reactivity with a cyanato group).
200 g (manufactured by Sumitomo Chemical Co., Ltd.) were 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 resin varnish for printed wiring board (solid content concentration = 28%).

Comparative Example 2 In Example 1, 210 g of polypropylene resin (manufactured by Wako Pure Chemical Industries), 1800 g of toluene, and 2,2-bis (4
-Cyanatephenyl) propane (Arocy B-1
0, manufactured by Asahi Ciba) 700 g and 11 g of nonylphenol (manufactured by Mitsui Chemicals) instead of p- (α-cumyl) phenol
10% toluene diluted solution of cobalt naphthenate (Co content = 8%, manufactured by Nippon Kagaku Sangyo Co., Ltd.) 4
g was added and the mixture was reacted at reflux temperature for 1 hour. Next, 190 g of a brominated bisphenol A type epoxy resin (ESB400, manufactured by Sumitomo Chemical Co., Ltd.) having reactivity with a cyanato group as a flame retardant was charged and melted. However, since the resin solution solidified (grease-like) near room temperature, toluene 90
0 g was further added and dissolved by stirring to produce a resin varnish for printed wiring board (solid content concentration = 29%).

Comparative Example 3 In Example 1, 210 g of polypropylene resin (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 1500 g of toluene, heated to 80 ° C. and dissolved by stirring, and then 2,2-bis (4-cyanatephenyl). Propane (Arocy B-10, manufactured by Asahi Ciba)
Instead of 2,2-bis (4-cyanatephenyl) propane oligomer (ArocyB-30, Asahi Ciba) 7
00 g, 67 g of nonylphenol instead of p- (α-cumyl) phenol, and a brominated bisphenol A type epoxy resin (E having reactivity with a cyanato group as a flame retardant) (E
SB400, Sumitomo Chemical Co., Ltd.)
It melt | dissolved by heating at 1 degreeC for 1 hour. Then cool to room temperature, and add 1 of zinc naphthenate (Zn content = 8%, manufactured by Nippon Kagaku Sangyo).
A resin varnish for printed wiring boards (solid content concentration = 44%) was manufactured by adding 3 g of a 0% toluene solution. However, in this resin varnish, an aggregated product of polypropylene resin was observed after 2 days.

Comparative Example 4 In Example 4, 1600 g of toluene, 300 g of polypropylene resin (manufactured by Wako Pure Chemical Industries, Ltd.), bis (3,5-dimethyl-4-cyanatophenyl) methane (ArocyM) were used.
-10, manufactured by Asahi Ciba) 600 g and 9 g of nonylphenol in place of p- (α-cumyl) phenol (manufactured by San Technochemical), dissolved with stirring and then manganese naphthenate (Mn content = 8%, manufactured by Japan Chemical Industry) 10% toluene solution (3 g) was added and reacted at reflux temperature for 1 hour. Next, as a flame retardant, tetrabromobisphenol A (Fireguard FG-200) having reactivity with a cyanato group is used.
0, manufactured by Teijin Kasei) was added and melted 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 resin varnish for printed wiring board (solid content concentration = 27%).

[0068]

[Table 1] (A) B-10 (manufactured by Asahi Ciba); 2,2-bis (4-cyanatophenyl) propane M-10 (manufactured by Asahi Ciba); bis (3,5-dimethyl-4-cyanatophenyl) methane F -10 (manufactured by Asahi Ciba); 2,2-bis (4-cyanatophenyl) -1,
1,1,3,3,3-Hexafluoropropane RTX-366 (manufactured by Asahi Ciba); α, α'-bis (4-cyanatophenyl) -m-diisopropylbenzene B-30 (manufactured by Asahi Ciba); 2 , 2-bis (4-cyanatophenyl)
Propane oligomer (B) PCP (manufactured by San Techno Chemical); p- (α-cumyl) phenol BPA (bisphenol A, manufactured by Mitsui Chemicals); 2,2-bis (4-
Hydroxyphenyl) propane NP (manufactured by Mitsui Chemicals); nonylphenol (C) polypropylene (manufactured by Wako Pure Chemical Industries); polypropylene resin (D) BCL-462 (manufactured by Albemarle); 1,2-dibromo-4-
(1,2-Dibromoethyl) cyclohexane BC-48 (manufactured by Albemarle); tetrabromocyclooctane CD-75P (manufactured by Great Lakes); hexabromocyclododecane SR-245 (manufactured by Daiichi Kogyo Seiyaku); 2,4,6 -Tris (tribromophenoxy) -1,3,5-triazine ESB-400 (Sumitomo Chemical Co., Ltd.); Brominated bisphenol A type epoxy resin TBA (FG-2000, Teijin Chemicals); Brominated bisphenol A (E) Co; 10% toluene solution of cobalt naphthenate (Co = 8%, manufactured by Japan Chemical Industry) Zn; zinc naphthenate (Zn = 8%, manufactured by Japan Chemical Industry)
10% toluene solution of Mn; manganese naphthenate (Mn = 8%, made by Nippon Kagaku Sangyo) 10% toluene solution Fe; iron naphthenate (Fe = 5%, made by Nihon Kagaku Sangyo) Cu; naphthene 10% toluene solution of copper acidate (Cu = 5%, manufactured by Nippon Kagaku Sangyo)

The obtained resin varnish for printed wiring board was 0.2
An E glass cloth having a thickness of mm was impregnated and heated at 140 ° C. for 5 to 10 minutes to obtain a prepreg having a resin adhesion amount of 40 to 45% by weight. In the case of the resin varnishes for printed wiring boards of Comparative Examples 1, 2 and 4, since the solid content concentration was low, the above impregnation coating operation was repeated twice to obtain a prepreg having a resin adhesion amount of 40 to 45% by weight. . In the prepreg of Comparative Example 3, separation of cyanate ester resin and polypropylene resin was observed. Next, four prepregs and 18 μm-thick copper foil were laminated on both sides, press-molded under conditions of 170 ° C. and 2.5 MPa for 60 minutes, and then heat-treated at 230 ° C. for 120 minutes to prepare a copper-clad laminate. The obtained copper-clad laminate was measured and evaluated for dielectric properties, solder heat resistance, copper foil peel strength and flame resistance by the following measurement methods. The results are shown in Table 2.

<Characteristics Evaluation Method> -Relative permittivity and dielectric loss tangent / 1 GHz: measured by the triplate structure linear line resonator method.・ Soldering heat resistance: PCT for test pieces with copper foil etched
After holding in (121 ° C., 0.22 MPa), 260
The appearance was examined by immersing in molten solder at 0 ° C. for 20 seconds. “OK” in the table means that no measling or swelling occurred. -Copper foil peel strength: measured according to JIS-C-6481. -Flame resistance: Measured according to UL-94 vertical test method.

[0071]

[Table 2]

As is clear from Table 2, the laminates using the resin compositions of Examples 1 to 5 have low relative permittivity and dielectric loss tangent at 1 GHz, solder heat resistance when absorbing moisture, and copper foil. Good peel strength. On the other hand, in the comparative example, when a phenol other than the present invention is used, a polypropylene resin is not blended, or a conventional flame retardant is used, the relative dielectric constant and the dielectric loss tangent at 1 GHz are increased, and the others, heat resistance, etc. I had a problem with.

[0073]

As described above, the modified cyanate resin varnish for a printed wiring board of the present invention has a low dielectric constant and a low dielectric loss tangent in a high frequency band, and has good solder heat resistance, adhesiveness and flame resistance, It is suitable as a resin varnish used for printed wiring boards of equipment that handles high-frequency signals. Further, the method for producing a prepreg for a laminated plate and a metal-clad laminated plate of the present invention has a low dielectric loss tangent in a high frequency band and is excellent in low loss, and the operating frequency of wireless communication-related terminal equipment, antennas, and microprocessors exceeds 1 GHz. It is suitable for a method for manufacturing a printed wiring board substrate used in such a high-speed computer.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C08L 79:00 C08L 79:00 F term (reference) 4F072 AD04 AD45 AE02 AE07 AF32 AG03 AG17 AG19 AH02 AH21 AJ04 AJ11 AK05 AK14 AL13 4F100 AB01A AB33A AK07B AK33B AK51B AK52K AL05B CA08B CA30B DH01B EJ82B GB43 JG05 JJ03 JJ07 JK06 4J038 DJ001 JA05 JA10 JA12 JA32 JA33 JB34 JC38 KA04 NA21 PB NA09 NA14

Claims (16)

[Claims] 1. A cyanate ester compound represented by formula (A) [1]: [Chemical 2] (In the formula, R ₄ and R ₅ represent a hydrogen atom or a lower alkyl group, and may be the same or different, and n is a positive integer of 1 to 2), (C) Polypropylene resin (D) Flame-retardant having no reactivity with cyanate ester compounds (E) Metal reaction catalyst (F) Aromatic hydrocarbon solvent and (G) Modified cyanate ester resin containing a ketone solvent as essential components Resin varnish for printed wiring boards. 2. One of (A) cyanate ester compounds
4 parts of (B) monohydric phenol compound to 100 parts by weight
A resin varnish for a printed wiring board, characterized in that the resin varnish is mixed in an amount of -30 parts by weight. 3. A modified cyanate ester resin obtained by reacting (A) a cyanate ester compound with (B) a part or all of a monohydric phenol compound, (C) a polypropylene resin, and (D) a cyanate ester. Flame retardant having no reactivity with the compound, (E) metal-based reaction catalyst,
The resin varnish for a printed wiring board according to claim 1 or 2, further comprising (F) an aromatic hydrocarbon solvent and (G) a ketone solvent as essential components. 4. The (A) cyanate ester compound is
2. One or a mixture of 2,2-bis (4-cyanatophenyl) propane and 2,2-bis (3,5-dimethyl-4-cyanatophenyl) methane.
4. A resin varnish for printed wiring boards according to any one of 3 to 3. 5. The (B) monohydric phenol compound is p-
The resin varnish for a printed wiring board according to claim 1, which is (α-cumyl) phenol. 6. The flame retardant having no reactivity with the (D) cyanate ester compound is 1,2-dibromo-4-
6. A printed wiring board according to claim 1, which is one of alicyclic flame retardants selected from (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane and hexabromocyclododecane or a mixture of two or more thereof. Resin varnish. 7. A flame retardant having no reactivity with a (D) cyanate ester compound is represented by the formula [3]: (In the formula, l, m, and n represent integers of 1 to 5, and may be the same or different, respectively) or a brominated triphenylcyanurate flame retardant or at least one or more thereof. 7. A resin varnish for printed wiring boards according to claim 1, which is a mixture of two or more kinds of a flame retardant having no reactivity with other cyanate ester compounds. 8. The (E) metal-based reaction catalyst is manganese, iron,
The resin varnish for a printed wiring board according to claim 1, which is one kind or two or more kinds selected from 2-ethylhexanoate, naphthenate and acetylacetone complex of cobalt, nickel, copper and zinc. 9. An aromatic hydrocarbon solvent (F) is used in an amount of 150 to 500 relative to 100 parts by weight of a polypropylene resin (C).
The resin varnish for a modified printed wiring board according to claim 1, wherein the resin varnish is heated and melted by using a part by weight. 10. The resin for a printed wiring board according to claim 1, wherein the ketone solvent (G) is used in an amount of 100 to 50 parts by weight based on 100 parts by weight of the aromatic hydrocarbon solvent (F). varnish. 11. The resin varnish for a printed wiring board according to claim 1, wherein the boiling point of the aromatic hydrocarbon solvent (F) is 70 to 170 ° C. 12. The resin varnish for a printed wiring board according to claim 1, wherein the aromatic hydrocarbon solvent (F) is at least one selected from the group consisting of toluene, xylene, ethylbenzene, isopropylbenzene and mesitylene. 13. The boiling point of (G) a ketone-based solvent is 50 to 1
It is 70 degreeC, The resin varnish for printed wiring boards of Claim 1 thru | or 12. 14. The (G) ketone solvent is one or more of any one of acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, methyl isobutyl ketone, 2-hexanone, cyclopentanone, 2-heptanone, and cyclohexanone. The resin varnish for a printed wiring board according to claim 1, which is used. 15. A base material is impregnated with the resin varnish for a printed wiring board according to claim 1, and then 80
To 200 ° C. Drying method for laminated prepreg characterized by the following: 16. A method for producing a metal-clad laminate, comprising stacking an arbitrary number of prepregs for laminates according to claim 15 and further stacking a metal foil on one surface or both surfaces thereof and heating under pressure.