JP2003327824A - Modified isocyante ester-based curing resin composition for laminated sheet, prepreg given by using the same, and the laminated sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curing resin composition from which a printed circuit board having good heat resistance, exhibiting such moldability and processability as similar to those of conventional heat-curing resin laminated sheets, and having a low dissipation factor in a high-frequency wave range so as to be excellently low in dielectric loss is obtained, to provide prepreg given by using the composition, and to provide a laminated sheet plated with metal. <P>SOLUTION: This modified isocyanate ester-based curing resin composition contains (A) isocyanate ester compounds, (B) monohydric phenol compounds, (C) a polybutadiene resin, (D) a flame-retardant which has no reactivity with the isocyanate ester compounds, and (E) a metal-based reaction catalyst as essential ingredients. The prepreg for the laminated sheet is formed by making the composition dissolved or dispersed in a solvent to obtain a resin varnish for the laminated sheet, immersing a base material in the varnish, and drying the immersed base material. The laminated sheet plated with the metal is formed by laminating pieces of the prepreg in an arbitrary number together with metal foil, then heating and pressurizing the laminated materials. <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 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. The present invention relates to a resin composition suitable for producing a board for a plate, a prepreg for a laminated board and a metal-clad laminated board using the resin composition. That is, the present invention relates to a modified cyanate ester-based curable resin composition having excellent high-frequency characteristics, a prepreg for a laminate and a metal-clad laminate using the same. 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 curable resin composition capable of producing an excellent high-density multilayer wiring board, a prepreg for a laminated board using the same, and a metal-clad laminated board.

[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 consists of a conductor loss determined by the shape of the wiring (conductor), skin resistance, characteristic impedance, etc. and a dielectric loss determined by the dielectric characteristics of the insulating layer (dielectric) around the wiring. Then, the influence of power loss due to dielectric loss is large. 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 signals 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, polyphenylene ether (PPO or PPE) disclosed in JP-B-5-77705 is disclosed.
Composition of resin and crosslinkable polymer / monomer and Japanese Patent Publication No. 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 Publication No. 5-77705 and Japanese Patent Publication No. 6-9
Although the method disclosed in Japanese Patent No. 2533 has an improved dielectric property, it has a problem that the resin composition has a high melt viscosity and lacks in fluidity since it is mainly composed of polyphenylene ether which is a thermoplastic polymer. . 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 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.

The resin composition prepared 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, has a low melt viscosity, 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 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) -135242). -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 characteristics and low dielectric loss tangent in a high frequency band. The present invention provides a curable resin composition capable of producing a high-density multilayer wiring board having excellent loss properties, a prepreg for a laminate and a metal-clad laminate using the same.

[0013]

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

[0014]

[Chemical 4]

[0015]

[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 )
Polybutadiene resin (D) Cyanate ester-based curable resin composition for laminated board, which contains a flame retardant having no reactivity with a cyanate ester compound and (E) a metal-based reaction catalyst as essential components

(2) The modified cyanate ester ester resin is blended with 4 to 30 parts by weight of the (B) monohydric phenol compound per 100 parts by weight of the (A) cyanate ester compound. ) A modified cyanate ester-based curable resin composition for a laminated plate as described above.

(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) Polybutadiene resin, (D) Cyanate ester compound and a flame retardant having no reactivity, and (E) a metal-based reaction catalyst are contained as essential components. A modified cyanate ester-based curable resin composition for a laminate.

(4) The cyanate ester compound (A) is either 2,2-bis (4-cyanatophenyl) propane or 2,2-bis (3,5-dimethyl-4-cyanatophenyl) methane. The modified cyanate ester-based curable resin composition for laminated plates according to the above (1) to (3), which is one kind or a mixture thereof.

(5) The modified cyanate ester-based curable resin composition for laminates according to the above (1) to (4), wherein the monohydric phenol compound (B) 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). A modified cyanate ester-based curable resin composition for a laminate.

(7) The flame retardant having no reactivity with the (D) cyanate ester compound is represented by the formula [3]

[0023]

[Chemical 6]

(In the formula, l, m and n represent integers of 1 to 5, and may be the same or different, respectively) or at least these flame retardants. The modified cyanate ester-based curable resin composition for laminated plates according to the above (1) to (6), which is a mixture of two or more kinds of one or more kinds and a flame retardant having no reactivity with other cyanate ester compounds.

(8) (E) The metal-based reaction catalyst is one or more selected from the group consisting of manganese, iron, cobalt, nickel, 2-ethylhexanoate, naphthenate and acetylacetone complex of zinc and zinc. A modified cyanate ester-based curable resin composition for laminates according to the above (1) to (7).

(9) The modified cyanate ester-based curable resin composition for laminates according to any one of (1) to (8) above is dissolved or dispersed in a solvent to form a varnish, and the varnish is impregnated into a substrate. Then, a prepreg for a laminate obtained by drying at 80 to 200 ° C.

(10) A metal-clad laminate obtained by stacking an arbitrary number of prepregs for laminates according to (9) above, further laminating a metal foil on the upper and lower surfaces or one surface, and heating and pressing.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention includes (A) a cyanate ester compound represented by the formula [1], (B) a monohydric phenol compound represented by the formula [2], (C) a polybutadiene resin, and (D). ) Modified cyanate ester-based curable resin composition for laminates having excellent high-frequency characteristics, which comprises a flame retardant having no reactivity with a cyanate ester compound and (E) a metal-based reaction catalyst as essential components, and a laminate using the same Prepreg and metal-clad laminate.

In addition to the above, the present invention provides (A) formula [1]
The modified cyanate ester resin obtained by reacting 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 modified cyanate ester-based curable resin composition for a laminate, which has a low dielectric loss tangent in a high frequency band and an excellent low loss property, and a prepreg for a laminate and a metal-clad laminate using the same.

Dielectric properties of polymer materials and the like are largely influenced by the orientation polarization of dipoles. Therefore, the dielectric constant can be lowered by reducing the polar groups in the molecule, and the dielectric loss tangent can be suppressed 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 impossible 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 composition of the present invention,
(B) A compound in which an appropriate amount of a monohydric phenol compound is blended to convert an unreacted cyanato group into an imide carbonate to reduce its polarity, thereby reducing the dielectric constant and dielectric loss tangent of a 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 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 (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 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 composition of the present invention, the blending amount of the monohydric phenol compound is important. That is,
When the blending amount is small, it cannot react with all the cyanato groups remaining as unreacted to reduce the polarity, and when the blending amount is larger than the necessary amount, it remains as unreacted and the hydroxyl group This is because the polarity deteriorates the dielectric properties of the cured product.

Further, in the resin composition of the present invention, the dielectric properties are improved by blending (C) polybutadiene resin, which is a thermoplastic resin having good dielectric properties, with the above modified cyanate ester resin. The cyanate ester resin and the polybutadiene 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) It was found that when a reaction of a monohydric phenol compound is carried out in a solvent solution of a polybutadiene resin, a so-called "semi-IPN" resin is produced and a uniform resin solution is obtained. Further, it is essential that the flame retardant used in the resin composition of the present invention has no reactivity with the cyanate ester compound so as not to inhibit the reaction between the (A) cyanate ester compound and the (B) monohydric phenol compound. Since it is a hydrocarbon-based 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 composition of the present invention comprises (A) a cyanate ester compound represented by the formula [1] and (B) a formula [2].
An essential component is a monohydric phenol compound represented by, (C) polybutadiene resin, (D) a flame retardant having no reactivity with cyanate ester compounds, and (E) a metal-based reaction catalyst. 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, 2,2-bis (3,5-dimethyl-4-cyanatophenyl) methane, 2,2-bis (4
-Cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, α, α'-bis (4-cyanatophenyl) -m-diisopropylbenzene, a cyanate ester of a phenol-added polystyrene polymer Etc. Among them, 2,2-bis (4-cyanatophenyl) propane and 2,2-bis (3,5-dimethyl-4-cyanatophenyl) 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 (B) monohydric phenol compound 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 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 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.

As the polybutadiene resin (C) in the present invention, those having a number average molecular weight of 500 to 5,000 or less are preferable because they have good compatibility and improve the dielectric properties. The blending amount of the (C) polybutadiene resin in the present invention is preferably 5 to 300 parts by weight, and 10 to 100 parts by weight of the (A) cyanate ester compound.
More preferably 200 parts by weight, 15 to 100
It is particularly preferable to use parts by weight. If the compounding amount of the (C) polybutadiene 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. In addition, the reactivity of the cyanate ester (A) 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 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 of the total amount of the (A) cyanate ester compound, the (B) monohydric phenol compound and the (C) polybutadiene 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. is there.

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 1-200 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, reactivity and curability tend to be insufficient, and if it exceeds 300 ppm, it becomes difficult to control the reaction, or curing becomes too fast and moldability deteriorates. Tends to become. The (E) metal-based reaction catalyst in the present invention may be added at the same time in a required amount as a reaction accelerator and a curing accelerator when the modified cyanate-based resin composition is produced. The amount of the catalyst necessary for promoting the modification reaction when producing the modified cyanate-based resin composition may be used, and the catalyst remaining after the reaction or another metal-based catalyst may be added and mixed as a curing accelerator.

In addition to the above-mentioned essential components, an inorganic filler and other additives can be added to the resin composition of the present invention as required. 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 blending amount is preferably 200 parts by weight or less based on 100 parts by weight of the total amount of the resin composition of the present invention. The resin composition of the present invention described above can be used, for example, in the production of a prepreg for printed wiring boards or a laminated board as follows. That is, the resin composition of the present invention is dissolved in a solvent to form a varnish, which is impregnated into a substrate such as glass cloth and dried to prepare a prepreg. Then, by laminating an arbitrary number of the prepregs and laminating metal foils on the upper and lower surfaces thereof or on one surface thereof and subjecting them to heat and pressure molding, a double-sided or single-sided metal-clad laminate can be obtained. Specific examples of the solvent used when varnishing the resin composition of the present invention include aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as trichloroethylene and chlorobenzene, and N, N-dimethyl. An amide-based solvent such as formamide or N, N-dimethylacetamide or a nitrogen-based solvent such as N-methylpyrrolidone is used. In particular, aromatic hydrocarbons such as benzene, toluene and xylene are more preferable. These solvents may be used alone or in combination of two or more. The compounding amount of the aromatic hydrocarbon solvent is (C) polybutadiene resin

150 to 500 parts by weight, preferably 150 to 400 parts by weight, more preferably 100 to 100 parts by weight,
Particularly preferred is 150 to 300 parts by weight. Further, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone have low solubility in the resin composition of the present invention, but when used in combination with the above solvents, a suspension solution of the resin composition of the present invention is produced. However, there is an advantage that a high-concentration and low-viscosity solution can be obtained. From this point of view, as the solvent used when varnishing the resin composition of the present invention, benzene, toluene, a mixture of aromatic hydrocarbons such as xylene and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone Solvents are particularly preferred. The compounding amount of the ketone solvent is 50 to 500 with respect to 100 parts by weight of the aromatic hydrocarbon solvent.
It is preferable to use parts by weight, more preferably 50 to 400 parts by weight, and particularly preferably 50 to 300 parts by weight.

[0047]

The present invention will be described in more detail with reference to the following examples. A varnish for laminated plate was manufactured according to the blending amount 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 polybutadiene resin (R-45HT, manufactured by Idemitsu Petrochemical) were charged and heated to 80 ° C. It was dissolved with stirring. Next, 2,2-bis (4-cyanatephenyl) propane (ArocyB
-10, manufactured by Asahi Ciba) 700 g, p- (α-cumyl) phenol (manufactured by San Techno Chemical) 64 g, brominated triphenyl cyanurate (Piroguard SR-245, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 135 g, dissolved and then naphthenic acid 4 g of a 10% toluene solution of cobalt (Co content = 8%, manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added and reacted at the 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, 1 g of a 10% toluene solution of zinc naphthenate (Zn content = 8%, manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added and dissolved by stirring to produce a resin varnish for a printed wiring board (solid content concentration = 51%). Was manufactured.

Example 2 300 g of toluene and 140 g of polybutadiene resin (R-45HT, manufactured by Idemitsu Petrochemical Co., 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, 2,2-bis (4-cyanatephenyl) propane (ArocyB
-10, manufactured by Asahi Ciba) 700 g, p- (α-cumyl) phenol (manufactured by San Techno Chemical) 10 g, brominated triphenyl cyanurate (Pyroguard SR-245, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 125 g, dissolved and then naphthenic acid 3 g of a 10% toluene solution of manganese (Mn content = 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., 600 g of methyl ethyl ketone (MEK) was added with stirring to suspend the reaction solution. After further cooling to room temperature, 75 g of p- (α-cumyl) phenol and zinc naphthenate (Zn content =
1% of a 10% toluene solution of 8%, manufactured by Nippon Kagaku Sangyo Co., Ltd. was added and dissolved by stirring to produce a resin varnish for printed wiring board (solid content concentration = 54%).

Example 3 300 g of toluene and 80 g of polybutadiene resin (R-45HT, manufactured by Idemitsu Petrochemical Co., 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, 800 g of α, α′-bis (4-cyanatophenyl) -m-diisopropylbenzene (RTX-366, manufactured by Asahi Ciba), p- (α
-Cumil) phenol (manufactured by San Techno Chemical) 10 g
2 g of a 10% toluene solution of iron naphthenate (iron content = 5%, manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added and reacted at reflux temperature for 1 hour, and then 1,2-dibromo-4-
(1,2-Dibromoethyl) cyclohexane (Sayt
110 g of exBCL-462, manufactured by Albemarle) 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, p-
75% (α-cumyl) phenol, 10% toluene solution of copper naphthenate (copper content = 5%, manufactured by Nippon Kagaku Sangyo) 2
g was added and dissolved by stirring to produce a resin varnish for printed wiring board (solid content concentration = 54%).

Example 4 600 g of toluene and 300 g of polybutadiene resin (R-45HT, manufactured by Idemitsu Petrochemical Co., 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. Then screw (3
5-dimethyl-4-cyanatophenyl) methane (Aro
CyM-10, manufactured by Asahi Ciba) 600 g, p- (α-cumyl) phenol (manufactured by San Techno Chemical Co., Ltd.) 30 g were charged and dissolved, and then a 10% toluene solution of cobalt naphthenate (Co content = 8%, manufactured by Nippon Kagaku Sangyo). 4 g was added and reacted at reflux temperature for 1 hour, and then 150 g of hexabromocyclododecane (CD-75P, manufactured by 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, p
120 g of-(α-cumyl) phenol was added and dissolved by stirring to produce a resin varnish for printed wiring boards (solid content concentration = 47%).

Example 5 750 g of toluene and 400 g of polybutadiene resin (R-45HT, manufactured by Idemitsu Petrochemical Co., 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, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3
Hexafluoropropane (ArocyF-10, manufactured by Asahi Ciba) 500 g, p- (α-cumyl) phenol (manufactured by San Techno Chemical) 28 g were charged and dissolved, and then copper naphthenate (Cu content = 5%, manufactured by Nippon Kagaku Sangyo) 10 g of a toluene solution of 6% was added and reacted at a reflux temperature for 1 hour, and then tetrabromocyclooctane (Saytex BC-4
(8, made by Albemarle) 150 g was added 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% toluene solution of manganese naphthenate (Mn content = 8%, manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added and dissolved by stirring to give a resin varnish for printed wiring board (solid content concentration = 46%). Manufactured.

Comparative Example 1 In Example 1, 210 g of polybutadiene resin (R-45HT, manufactured by Idemitsu Petrochemical) was added to 1800 g of toluene.
2,2-bis (4-cyanatephenyl) propane (A
rocyB-10, manufactured by Asahi Ciba) 700 g and p- (α-
Instead of (cumyl) phenol, 69 g of 2,2-bis (4-hydroxyphenyl) propane (BPA; bisphenol A, manufactured by Mitsui Toatsu Kagaku Co., Ltd.) was charged, and after stirring and dissolving, cobalt naphthenate (Co content = 8%, Japan Made by chemical industry)
3 g of a 10% diluted solution of toluene in 1 was added at the reflux temperature to 1
Reacted for hours. Then, 200 g of a brominated bisphenol A type epoxy resin (ESB400, manufactured by Sumitomo Chemical Co., Ltd.) having reactivity with a cyanenato group as a flame retardant was charged and melted. 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 concentration = 28
%) Was produced.

Comparative Example 2 In Example 1, 210 g of polybutadiene resin (R-45HT, manufactured by Idemitsu Petrochemical) was added to 1800 g of toluene.
2,2-bis (4-cyanatephenyl) propane (A
rocyB-10, manufactured by Asahi Ciba) 700 g and p- (α-
Cumyl) 11 g of nonylphenol (manufactured by Mitsui Toatsu Chemical Co., Ltd.) was added instead of phenol, and after stirring and dissolving, 10% of cobalt naphthenate (Co content = 8%, manufactured by Nippon Kagaku Sangyo)
4 g of a diluted solution of toluene was added and the reaction was carried out at the reflux temperature for 1 hour. Then, as a flame retardant, a brominated bisphenol A type epoxy resin (ESB4
00, manufactured by Sumitomo Chemical Co., Ltd.), and melted. However, since the resin solution solidified (grease-like) around room temperature, 900 g of toluene 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 polybutadiene resin (R-45HT, manufactured by Idemitsu Petrochemical Co., Ltd.) was added to 1500 g of toluene, heated to 80 ° C. and dissolved by stirring, and then 2,2-bis (4-). Cyanate phenyl) propane (ArocyB-
10, 2, Asahi Ciba) instead of 2,2-bis (4-cyanate phenyl) propane oligomer (ArocyB-3
0, manufactured by Asahi Ciba) 700 g, 67 g of nonylphenol instead of p- (α-cumyl) phenol, and brominated bisphenol A having reactivity with a cyanenato group as a flame retardant.
Type epoxy resin (ESB400, Sumitomo Chemical Co., Ltd.) 200
g was added and the mixture was heated and dissolved at 80 ° C. for 1 hour. Then, the mixture was cooled to room temperature, and 3 g of a 10% toluene solution of zinc naphthenate (Zn content = 8%, manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added to produce a resin varnish for printed wiring boards (solid content concentration = 44%). However, in this resin varnish, aggregated separation products of polystyrene resin were observed after 2 days.

Comparative Example 4 In Example 4, 1600 g of toluene, 300 g of polybutadiene resin (R-45HT, manufactured by Idemitsu Petrochemical), bis (3,5-dimethyl-4-cyanatophenyl) methane (ArocyM-10, Asahi Ciba) Made) 600 g and p-
9 g of nonylphenol was added in place of (α-cumyl) phenol (manufactured by San Techno Chemical), and after stirring and dissolution, 3 g of 10% toluene solution of manganese naphthenate (Mn content = 8%, manufactured by Nippon Kagaku Sangyo) was added and refluxed. 1 at temperature
Reacted for hours. Then, as a flame retardant, 150 g of tetrabromobisphenol A (Fireguard FG-2000, manufactured by Teijin Kasei) having reactivity with a cyanenato 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 resin varnish for printed wiring board (solid content concentration =
27%).

[0056]

[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)
Oligomer of propane (B) PCP (manufactured by San Techno Chemical); p- (α-cumyl) phenol BPA (bisphenol A, manufactured by Mitsui Toatsu Chemical); 2,2-bis (4-hydroxyphenyl) propane NP (Mitsui Toatsu) Nonylphenol (C) R-45HT (manufactured by Idemitsu Petrochemical); Polybutadiene 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 oxide (Cu = 5%, manufactured by Nippon Kagaku Sangyo Co., Ltd.) The obtained resin varnish for a printed wiring board is impregnated into an E glass cloth having a thickness of 0.2 mm and heated at 140 ° C. for 5 to 10 minutes. A prepreg having a resin adhesion amount of 40 to 45% by weight was obtained. 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 polybutadiene resin was observed. Next, 4 prepregs and 18 μm thick copper foil are laminated on both sides, and 170
After press molding for 60 minutes under the conditions of ℃ and 2.5 MPa, 2
It heat-processed at 30 degreeC for 120 minutes, and produced the copper clad laminated board.
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.

[0058]

[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 during moisture absorption, and copper foil peel strength. Is good. On the other hand, in the comparative example, the relative dielectric constant and dielectric loss tangent at 1 GHz were high, and there was a problem in heat resistance.

[0059]

INDUSTRIAL APPLICABILITY As described above, the modified cyanate meter resin composition of the present invention has a low dielectric constant or dielectric loss tangent in a high frequency band, good soldering heat resistance, adhesiveness, and flame resistance, and exhibits high frequency signals. It is suitable as a resin composition for laminated boards used for printed wiring boards of devices to be handled. Further, the prepreg for a laminated plate and the metal-clad laminated plate of the present invention have a low dielectric loss tangent in a high frequency band and an excellent low loss property, and an operating frequency of a terminal device, an antenna and a microprocessor related to wireless communication is several hundred MH.
It is suitable for manufacturing a substrate for a printed wiring board used for a high speed computer exceeding z.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/13 C08K 5/13 5/3492 5/3492 C08L 47/00 C08L 47/00 F term (reference) 4F072 AD04 AD11 AE01 AE07 AF12 AF14 AF17 AF20 AF32 AG03 AG17 AH02 AH22 AJ04 AK05 AK14 AL13 4F100 AB01B AB01C AB33B AB33C AK29A AK51A AL05A BA02 BA03 BA10B BA10C CA08A CA30A DH01A EJ82A GB43 4J002 BC113 BL01X CG033 CM02W EB097 ED077 EJ026 EU187 FD010 FD133 FD137 FD206 GF00 GQ00

Claims (10)

[Claims] 1. A cyanate ester compound represented by formula (A) [1]: [Chemical 2] (In the formula, R ₄ and R ₅ each represent a hydrogen atom or a lower alkyl group, and may be the same or different. N is a positive integer of 1 to 2), (C) polybutadiene resin (D) A modified cyanate ester-based curable resin composition for laminated plates, which contains a flame retardant having no reactivity with a cyanate ester compound and (E) a metal-based reaction catalyst as essential components. 2. The modified cyanate ester ester resin is blended with 4 to 30 parts by weight of the monohydric phenol compound (B) per 100 parts by weight of the cyanate ester compound (A). The modified cyanate ester-based curable resin composition for a laminated plate of. 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 polybutadiene resin, and (D) a cyanate ester. The modified cyanate ester-based curable resin composition for laminated plates according to claim 1 or 2, which contains a flame retardant having no reactivity with the compound and (E) a metal-based reaction catalyst 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 modified cyanate ester-based curable resin composition for laminated plates according to any one of 3 to 3. 5. The (B) monohydric phenol compound is p-
The modified cyanate ester-based curable resin composition for laminates 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 modified laminate for laminates 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. Cyanate ester-based curable resin composition. 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 modified cyanate ester-based curable resin composition for a laminate 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 modified cyanate ester-based curable resin composition for laminated plates 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. object. 9. A varnish prepared by dissolving or dispersing the modified cyanate ester-based curable resin composition for laminates according to claim 1 in a solvent, and impregnating the varnish with a substrate, A prepreg for a laminate obtained by drying at 80 to 200 ° C. 10. A metal-clad laminate obtained by stacking an arbitrary number of prepregs for laminates according to claim 9 and further laminating a metal foil on the upper and lower surfaces or one side thereof and heating and pressing.