JP2002146185A - Modified cyanate ester-based curable resin composition for laminate the prepreg and laminate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable resin composition having excellent heat resistance, exhibiting moldability and processability similar to those of a conventional thermosetting resin laminate, providing a printed-wiring board having a low dielectric dissipation factor in a high-frequency band and excellent low loss and a prepreg for a laminate and a metal-clad laminate using the same. SOLUTION: This modified cyanate ester-based curable resin composition comprises (A) a cyanate ester compound, (B) a monohydric phenol compound, (c) a polyethylene resin, (D) a flame retardant having no reactively to the cyanate ester compound and (E) a metal-based reaction catalyst as essential components. This prepreg is obtained by dissolving or dispersing the composition in a solvent to give a resin varnish for a laminate, impregnating the varnish into a substrate and drying the varnish. This metal-clad laminate is obtained by laminating an arbitrary number of the prepreg for a laminate to a metal foil and pressurizing the laminate under heating.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printed wiring used in terminal equipment and antennas for wireless communication requiring low loss in a high frequency band, and high-speed computers in which the operating frequency of a microprocessor exceeds several hundred MHz. The present invention relates to a resin composition suitable for producing a board for a board, a prepreg for a laminate, and a metal-clad laminate using the same. That is, the present invention relates to a modified cyanate ester-based curable resin composition having excellent high-frequency characteristics, and a prepreg for a laminate and a metal-clad laminate using the same.

More specifically, it has good heat resistance, exhibits moldability and workability similar to conventional thermosetting resin laminates such as epoxy resins, and has low dielectric properties, especially low dielectric loss tangent in a high frequency band. The present invention relates to 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.

[0003]

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

The transmission loss in a printed wiring board is caused by the wiring (conductor)
And the dielectric loss determined by the dielectric properties of the insulating layer (dielectric) around the wiring, and the power loss due to the dielectric loss is large in a high-frequency circuit. Therefore, it is considered necessary to reduce the dielectric constant and the dielectric loss tangent (tan δ) of the printed wiring board substrate (especially insulating resin) in order to reduce the transmission loss of the high-frequency circuit. For example, in a mobile communication related device that handles a high-frequency signal, a substrate having a low dielectric loss tangent is strongly desired in order to reduce a transmission loss in a quasi-microwave band (1 to 3 GHz) as the signal becomes higher in frequency. I have.

In electronic information devices such as computers, high-speed microprocessors whose operating frequency exceeds 200 MHz and high-frequency signals have been developed in order to process a large amount of information in a short time. In a device handling such a high-speed pulse signal, a delay on a printed wiring board has become a problem. Since the signal delay time in a printed wiring board becomes longer in proportion to the square root of the relative permittivity εr of the insulator around the wiring, a resin for a substrate having a low dielectric constant is required for a wiring board used in a computer or the like.

As a resin composition for improving the high-frequency characteristics of a printed wiring board in response to the above-mentioned increase in signal frequency, a composition using a cyanate ester resin having the lowest dielectric constant among thermosetting resins has been proposed. There is a method using a cyanate ester / epoxy resin composition disclosed in JP-A-46-41112 and a bismaleimide / cyanate ester / epoxy resin composition disclosed in JP-B-52-31279.

[0007] In order to improve high-frequency characteristics by using a thermoplastic resin, a polyphenylene ether (PPO or PPE) disclosed in Japanese Patent Publication No. 5-77705 has been proposed.
Resin composition of styrene and crosslinkable polymer / monomer and JP-B-6-
Polyphenylene ether-based resin compositions 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 Is used.

Further, as a resin composition comprising a cyanate ester resin having a low dielectric constant and a polyphenylene ether having a good dielectric property, a resin composition comprising a cyanate ester disclosed in Japanese Patent Publication No. 33506/1988 is disclosed. There is a method using a resin composition of bismaleimide and polyphenylene ether, and a resin composition of a phenol-modified resin / cyanate ester reactant and polyphenylene ether described in JP-A-5-311071. Furthermore, as a heat-resistant molding material with good high-frequency characteristics,
As disclosed in JP-B-61-18937, there is a resin composition obtained by kneading a cyanate ester resin with polyphenylene ether.

[0009]

[Problems to be Solved by the Invention] Japanese Patent Publication No. 46-4111
The method disclosed in Japanese Patent Publication No. 2 and JP-B-52-31279 has a problem that although the dielectric constant is slightly lowered, it contains a thermosetting resin other than the cyanate ester resin and thus has insufficient high frequency characteristics. there were.

[0010] Japanese Patent Publication No. 5-77705 and Japanese Patent Publication No. 6-9
The method disclosed in Japanese Patent No. 2533 has a problem that, although the dielectric properties are improved, the melt viscosity of the resin composition is high and the fluidity is insufficient because the resin is mainly composed of polyphenylene ether which is originally a thermoplastic polymer. . Therefore, the moldability is poor and unsuitable for manufacturing a multilayer printed wiring board that requires high temperature and high pressure when press-forming a laminated board or that needs to fill in the grooves between fine circuit patterns.

[0011] JP-B-63-33506 and JP-A-5-33506
In the method disclosed in Japanese Patent No. 310771, since the thermosetting resin used in combination with polyphenylene ether is a bismaleimide / cyanate ester resin or a phenol-modified resin / cyanate ester reactant, the high-frequency characteristics are still improved although the dielectric characteristics are slightly improved. There was a problem that it was insufficient. When the amount of polyphenylene ether is increased to improve the high-frequency characteristics, the melt viscosity of the resin composition becomes high and the fluidity becomes insufficient similarly to the above-mentioned polyphenylene ether-based resin composition. There was a point.

A resin composition obtained by kneading polyphenylene ether disclosed in Japanese Patent Publication No. 18937/1986 has good dielectric properties and, when modified with a cyanate ester resin, has a low melt viscosity. Although the properties are relatively good, the use of a cyanate ester alone as a curable component tends to increase the dielectric properties of the cured resin in that the dielectric loss tangent is higher than the value of the dielectric constant. There was a problem that it could not be reduced sufficiently. Furthermore, if the compounding amount of the cyanate ester is reduced to increase the dielectric loss tangent (the compounding amount of the polyphenylene ether is increased), the melt viscosity of the resin composition becomes high similarly to the above-mentioned polyphenylene ether-based resin composition, and the fluidity is insufficient. Therefore, there is a problem that the moldability is poor.

In view of such circumstances, the present inventors have proposed a method in which a composition obtained by modifying a specific cyanate ester resin with a monohydric phenol compound is used for a part or all of a matrix resin (Japanese Patent Application No. Hei. No. -80033). However, a particular cyanate ester resin is
Although a resin composition having good high-frequency characteristics could be obtained by modification with a polyhydric phenol compound, there was a problem that the specific cyanate ester resin used was special and expensive.

The present invention has good heat resistance, has moldability and workability similar to those of conventional thermosetting resin laminates such as epoxy resin, and has low dielectric properties and low dielectric loss tangent in a high frequency band. An object of the present invention is to provide a curable resin composition capable of producing a high-density multilayer wiring board excellent in loss property, and a prepreg for a laminate and a metal-clad laminate using the same.

[0015]

The present invention relates to (A) a cyanate ester compound represented by the formula [1], (B)
High-frequency characteristics comprising, as essential components, a monohydric phenol compound represented by the formula [2], a flame retardant having no reactivity with (C) a polyethylene resin, (D) a cyanate ester compound, and (E) a metal-based reaction catalyst. A modified cyanate ester-based curable resin composition for laminates, and a prepreg for laminates and a metal-clad laminate using the same.

Still further, the present invention provides a compound of the formula (1)
(B) using a modified cyanate ester resin obtained by reacting 4 to 30 parts by weight of a monohydric phenol compound represented by the formula [2] with respect to 100 parts by weight of the cyanate ester compound represented by the formula (2). A modified cyanate ester-based curable resin composition for a laminate, which has a low dielectric loss tangent in a high frequency band and is excellent in low loss property, a prepreg for a laminate, and a metal-clad laminate using the same.

The dielectric properties of polymer materials and the like are greatly affected by the orientation polarization of the dipole. Therefore, the dielectric constant can be reduced by reducing the number of polar groups in the molecule, and the dielectric loss tangent can be reduced by suppressing the mobility of the polar groups. Can be reduced. The cyanate ester resin has a strong polar cyanato group, but generates a symmetric and rigid triazine structure during curing, 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 as the curing reaction proceeds, the reaction system becomes fluid. And remains in the system as an unreacted cyanato group.
As a result, hitherto, only a cured product having a higher dielectric constant and a higher dielectric tangent than the original cured product has been obtained.

On the other hand, in the resin composition of the present invention,
(B) An attempt is made to lower the dielectric constant and dielectric loss tangent of a cured product by mixing an appropriate amount of a monohydric phenol compound to convert an unreacted cyanato group into imide carbonate to reduce its polarity. As a material used for this purpose, a compound having high reactivity with a cyanato group, a monofunctional compound having a relatively low molecular weight, and having good compatibility with a cyanate ester resin (having similarity in molecular structure) is suitable. It is thought that there is. The monohydric phenol compound used in the resin composition of the present invention is a compound specified for such a reason.

Conventionally, a phenol compound such as nonylphenol has been used as a co-catalyst for the trimerization reaction of cyanate ester (formation of a triazine ring).
About 1 to 2 parts by weight based on parts by weight was used. However, since the compounding amount was a catalytic amount, the effect of lowering the polarity by reacting with the unreacted cyanato group as described above was not recognized. However, the present inventors examined the amount of the phenolic compound, and found that the incorporation of a larger amount of the phenolic compound lowers the dielectric constant and the dielectric loss tangent of the cured product. It has been found that if a compound is used, a decrease in heat resistance due to an increase in the compounding amount can be suppressed. Therefore, according to the method of the present invention, a cured product of a conventional cyanate ester resin alone, a conventional epoxy resin or a polyhydric phenol (one of the hydroxyl groups is likely to remain as an unreacted group, so that the dielectric properties are rather deteriorated) and A cured product having a lower dielectric constant and a lower dielectric loss tangent than a cured product of a resin containing bismaleimide or the like can be obtained.

Therefore, in the resin composition of the present invention, the amount of the monohydric phenol compound is important. That is,
If the compounding amount is small, it reacts with all the cyanato groups remaining as unreacted and cannot be reduced in polarity, and if the compounding amount is larger than the required amount, it itself remains unreacted and its own 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) a polyethylene resin which is a thermoplastic resin having good dielectric properties with the above-mentioned modified cyanate ester resin. The cyanate ester resin and the polyethylene resin are originally incompatible with each other and it is difficult to obtain a uniform resin. However, according to the method found by the present inventors, (A) the cyanate ester compound and (B) ) When the reaction of a monohydric phenol compound is carried out in a solvent solution of a polyethylene resin, a so-called "semi-IP"
It was found that an N ″ -formed resin was formed and a uniform resin solution was obtained.

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 (A) the cyanate ester compound and (B) the monohydric phenol compound. Is essential, and since it is a hydrocarbon-based low-polarity compound, it hardly deteriorates the dielectric properties of the cured product. Another type of flame retardant, even if it is a compound other than a hydrocarbon compound, has a triazine structure similar to that of a cured product of a cyanate ester, so it is easily compatible with a cured product of a cyanate ester resin, and has heat resistance and dielectric properties. Can be imparted without deteriorating the flame resistance.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition of the present invention comprises (A) a cyanate ester compound represented by the formula [1];
Essential components are a monohydric phenol compound represented by the formula [2], (C) a polyethylene resin, (D) a flame retardant having no reactivity with a cyanate ester compound, and (E) a metal-based reaction catalyst.

The (A) cyanate ester compound 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, for example, bis (4
-Cyanatophenyl) ethane, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (3,5-dimethyl-4-cyanatophenyl) methane, 2,2-bis (4-cy Anatophenyl) -1,1,1,3,3,3-
Examples thereof include hexafluoropropane, α, α′-bis (4-cyanatophenyl) -m-diisopropylbenzene, and a cyanate ester of a phenol-added polystyrene polymer. Among them, 2,2-bis (4-cyanatophenyl) propane and 2,2-bis (3,5-dimethyl-4-cyanatophenyl) are more preferable. As the cyanate ester compound (A), one type may be used alone, or two or more types may be used in combination.

The (B) monohydric phenol compound in the present invention is a monohydric phenol represented by the formula [2]:
Compounds having good heat resistance are preferred. Examples of the compound represented by the formula [2] include p- (α-cumyl) phenol. In addition, as the (B) monohydric phenol compound, one kind may be used alone, or two or more kinds may be used in combination.

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

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

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

As the polyethylene resin (C) in the present invention, a resin having a density of 0.94 or more is preferable for improving the dielectric properties.

The amount of the polyethylene resin (C) in the present invention is preferably 5 to 300 parts by weight based on 100 parts by weight of the cyanate ester compound (A).
More preferably 10 to 200 parts by weight, 15 to 15 parts by weight
Particularly preferred is 100 parts by weight. (C) If the blending amount of the polyethylene resin is less than 5 parts by weight, sufficient dielectric properties tend not to be obtained, and if it exceeds 300 parts by weight, the melt viscosity of the resin becomes high and fluidity becomes insufficient, so that moldability is poor. In addition, the reactivity of the cyanate esters (A) tends to deteriorate.

Examples of the flame retardant having no reactivity with the cyanate ester compound (D) in the present invention include:
1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclohexane, hexabromocyclododecane, polybromodiphenyl ether,
Brominated polystyrene, brominated polycarbonate and brominated triphenyl cyanate-based flame retardant represented by the formula [3] are exemplified. Among them, 1,2-dibromo-4 is preferable.
-(1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane,
2,4,6-tris (tribromophenoxy) -1,
3,5-triazine and the like are more preferred.

In the present invention, the compounding amount of the flame retardant having no reactivity with the cyanate ester compound (D) is (A)
The total amount of the cyanate ester compound, (B) the monohydric phenol compound and (C) the polyethylene resin is preferably 5 to 30 parts by weight, and more preferably 5 to 30 parts by weight.
It is more preferably 0 parts by weight, particularly preferably 10 to 20 parts by weight. (D) If the compounding amount of the flame retardant having no reactivity with the cyanate ester compound 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 comprises (A)
It promotes the reaction between the cyanate ester compound and the (B) monohydric phenol compound, and is used as a reaction catalyst when producing a modified cyanate resin composition and a curing accelerator when producing a laminate. . Metal-based reaction catalysts include manganese, iron, cobalt, nickel, copper,
A metal catalyst such as zinc is used, and specifically, an organic metal salt compound such as 2-ethylhexanoate and naphthenate and an organic metal complex such as an acetylacetone complex are used. The same metal-based reaction catalyst may be used alone in the reaction accelerator for producing the modified cyanate-based resin composition and the curing accelerator for producing the laminate, or using two or more different types each. Is also good.

In the present invention, the amount of the metal-based reaction catalyst (E) is 1 to the cyanate ester compound (A).
To 300 ppm, preferably 1 to 200 pp
m, more preferably 2 to 150 ppm. (E) If the amount of the metal-based reaction catalyst is less than 1 ppm, the reactivity and curability tend to be insufficient. If the amount exceeds 300 ppm, the control of the reaction becomes difficult, and the curing becomes too fast, resulting in poor moldability. Tend to be. In the compounding of the metal-based reaction catalyst (E) in the present invention, the amounts required as a reaction accelerator and a curing accelerator in producing the modified cyanate-based resin composition may be simultaneously combined. When the modified cyanate-based resin composition is produced, an amount necessary for accelerating the modification reaction may be used, and after completion of the reaction, the remaining catalyst or another metal-based catalyst may be added and mixed as a curing accelerator.

The resin composition of the present invention may contain, if necessary, an inorganic filler and other additives in addition to the above essential components. As the filler, silica, alumina,
Aluminum hydroxide, calcium carbonate, clay, talc, silicon nitride, boron nitride, titanium oxide, barium titanate, lead titanate, strontium titanate and the like can be used. The 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 is used, for example, for producing a prepreg or a laminate for a printed wiring board as described below. That is, first, a prepreg is prepared by dissolving the resin composition of the present invention in a solvent to form a varnish, impregnating a substrate such as a glass cloth, and drying. Then, any number of the prepregs are stacked, and a metal foil is stacked on the upper or lower surface or one surface thereof, and is heated and pressed to form a double-sided or single-sided metal-clad laminate.

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; N
Amide-based solvents such as -dimethylformamide and N, N-dimethylacetamide, and nitrogen-based solvents such as N-methylpyrrolidone are used. Particularly, aromatic hydrocarbons such as benzene, toluene and xylene are more preferable. These solvents may be used alone or as a mixture of two or more. The blending amount of the aromatic hydrocarbon solvent is
(C) 150 to 150 parts by weight of polyethylene resin
500 parts by weight is preferable, 150 to 400 parts by weight is more preferable, and 150 to 300 parts by weight is particularly preferable.

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-mentioned solvents, a suspension of the resin composition of the present invention is used. To produce a solution having a high concentration and a low viscosity. From this viewpoint, as a solvent used when varnishing the resin composition of the present invention, a mixture of aromatic hydrocarbons such as benzene, toluene and xylene with ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone is used. Solvents are particularly preferred. The amount of the ketone solvent is preferably 50 to 500 parts by weight based on 100 parts by weight of the aromatic hydrocarbon solvent.
50 to 400 parts by weight is more preferable, and 50 to 300 parts by weight is particularly preferable.

[0040]

The present invention will be described in more detail with reference to the following examples. Varnishes for laminates were manufactured according to the amounts shown in Table 1.

Example 1 450 g of toluene and 210 g of a polyethylene resin (XM-220, manufactured by Mitsui Petrochemical) were charged into a 5-liter four-neck separable flask equipped with a thermometer, a cooling pipe, and a stirrer. And dissolved by stirring. Next, 2,2-bis (4-cyanatephenyl) propane (ArocyB-
10, 700 g of Asahi Ciba), 64 g of p- (α-cumyl) phenol (manufactured by San Techno Chemical), and 135 g of brominated triphenylcyanurate (Piroguard SR-245, manufactured by Daiichi Kogyo Seiyaku) are added and dissolved, followed by cobalt naphthenate. 4 g of a 10% toluene solution (Co content = 8%, manufactured by Nippon Kagaku Sangyo) was added and reacted at 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. After further cooling to room temperature, 1 g of a 10% toluene solution of zinc naphthenate (Zn content = 8%, manufactured by Nippon Kagaku Sangyo) was added and dissolved by stirring, followed by resin varnish for printed wiring boards (solids concentration = 51%). Was manufactured.

Example 2 300 g of toluene and 140 g of polyethylene resin (XM-220, manufactured by Mitsui Petrochemical) were charged into a 5-liter four-neck separable flask equipped with a thermometer, a cooling pipe, and a stirrer. And dissolved by stirring. Next, 2,2-bis (4-cyanatephenyl) propane (ArocyB-
10, 700 g of p- (α-cumyl) phenol (manufactured by San Techno Chemical) and 125 g of brominated triphenylcyanurate (Piroguard SR-245, manufactured by Daiichi Kogyo Seiyaku) were added and dissolved, and then manganese naphthenate was added. 3 g of a 10% toluene solution (Mn content = 8%, manufactured by Nippon Kagaku Sangyo) was added and reacted at 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. After further cooling to room temperature, 75 g of p- (α-cumyl) phenol and zinc naphthenate (Zn content =
1 g of a 10% toluene solution of 8% (manufactured by Nippon Chemical Industry Co., Ltd.) was added and dissolved by stirring to produce a resin varnish for printed wiring boards (solid content concentration = 54%).

Example 3 300 g of toluene and 80 g of a polyethylene resin (XM-220, manufactured by Mitsui Petrochemical) were charged into a 5-liter four-neck separable flask equipped with a thermometer, a condenser, and a stirrer. And dissolved by stirring. Next, 800 g of α, α′-bis (4-cyanatophenyl) -m-diisopropylbenzene (RTX-366, manufactured by Asahi Ciba) and p- (α-
After adding and dissolving 10 g of cumyl) phenol (manufactured by San Techno Chemical), 2 g of a 10% toluene solution of iron naphthenate (iron content = 5%, manufactured by Nippon Kagaku Sangyo) was added and reacted at reflux temperature for 1 hour. 2-dibromo-4- (1,
2-dibromoethyl) cyclohexane (Saytex B
(CL-462, manufactured by Albemarle) 110 g was added and dissolved. 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. After further cooling to room temperature, p- (α-
75 g of cumyl) phenol, copper naphthenate (copper content =
2 g of a 10% toluene solution of 5% (manufactured by Nippon Kagaku Sangyo) was added and dissolved by stirring to produce a resin varnish for printed wiring boards (solids concentration = 54%).

Example 4 600 g of toluene and 300 g of polyethylene resin (XM-220, manufactured by Mitsui Petrochemical) were charged into a 5-liter four-neck separable flask equipped with a thermometer, a cooling pipe, and a stirrer. And dissolved by stirring. Next, screw (3,5
-Dimethyl-4-cyanatophenyl) methane (Aroc
yM-10, manufactured by Asahi Chiba) 600 g, p- (α-cumyl)
After adding and dissolving 30 g of phenol (manufactured by San Techno Chemical), 4 g of a 10% toluene solution of cobalt naphthenate (Co content = 8%, manufactured by Nippon Kagaku Sangyo) was added and reacted at reflux temperature for 1 hour, and then hexabromocyclododecane was added. 150 g (CD-75P, manufactured by Great Lakes) was charged 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. After further cooling to room temperature, p-
120 g of (α-cumyl) phenol was added and dissolved by stirring to prepare a resin varnish for printed wiring boards (solids concentration = 47%).

Example 5 A 750 g of toluene and 400 g of a polyethylene resin (XM-220, manufactured by Mitsui Petrochemical) were charged into a 5-liter four-neck separable flask equipped with a thermometer, a cooling pipe, and a stirrer. And dissolved by stirring. Next, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-
After adding and dissolving 500 g of hexafluoropropane (ArocyF-10, manufactured by Asahi Ciba) and 28 g of p- (α-cumyl) phenol (manufactured by San Techno Chemical), copper naphthenate (Cu content = 5%, manufactured by Nippon Chemical Industry) was added. 6 g of a 10% toluene solution was added and reacted at the reflux temperature for 1 hour. Then, tetrabromocyclooctane (Saytex BC-4) was added.
8, 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 mixture. After cooling to room temperature, 1 g of a 10% toluene solution of manganese naphthenate (Mn content = 8%, manufactured by Nippon Kagaku Sangyo) was added and dissolved by stirring to obtain a resin varnish for printed wiring boards (solids concentration = 46%). Manufactured.

Comparative Example 1 In Example 1, 210 g of a polyethylene resin (XM-220, manufactured by Mitsui Petrochemical) was added to 1,800 g of toluene.
2-bis (4-cyanatephenyl) propane (Aro
700 g of cyB-10 (manufactured by Asahi Chiba) and 69 g of 2,2-bis (4-hydroxyphenyl) propane (BPA; bisphenol A, manufactured by Mitsui Toatsu Chemicals) instead of p- (α-cumyl) phenol were added. After stirring and dissolving, 10 parts of cobalt naphthenate (Co content = 8%, manufactured by Nippon Chemical Industry)
3 g of a 1% toluene diluted solution was added and reacted at a reflux temperature for 1 hour. Next, a brominated bisphenol A type epoxy resin (ESB) having a reactivity with a cyanate group as a flame retardant
(200, manufactured by Sumitomo Chemical Co., Ltd.). However, since the resin solution was solidified (grease-like) at around normal temperature, 1200 g of toluene was further added thereto and dissolved by stirring to produce a resin varnish for printed wiring boards (solid content: 28%).

Comparative Example 2 In Example 1, 210 g of a polyethylene resin (XM-220, manufactured by Mitsui Petrochemical) was added to 1800 g of toluene.
2-bis (4-cyanatephenyl) propane (Aro
700 g of cyB-10 (manufactured by Asahi Chiba) and 11 g of nonylphenol (manufactured by Mitsui Toatsu Chemicals) instead of p- (α-cumyl) phenol were stirred and dissolved, and cobalt naphthenate (Co content = 8%, Nippon Chemical) (Manufactured by Sangyo Co., Ltd.) was added and reacted at reflux temperature for 1 hour. Next, a brominated bisphenol A type epoxy resin (ESB40) having a reactivity with a cyanate group as a flame retardant is used.
(0, manufactured by Sumitomo Chemical Co., Ltd.), and 190 g was melted and cooled.
However, since the resin solution solidified (greased) at around normal temperature, 900 g of toluene was further added and dissolved by stirring to produce a resin varnish for printed wiring boards (solids concentration = 29%).

Comparative Example 3 In Example 1, 210 g of a polyethylene resin (XM-220, manufactured by Mitsui Petrochemical) was charged into 1500 g of toluene, heated to 80 ° C. and stirred to dissolve, and then 2,2-bis (4
-Cyanatephenyl) propane (ArocyB-1)
0, manufactured by Asahi Chiba) instead of an oligomer of 2,2-bis (4-cyanatephenyl) propane (ArocyB-3)
0, manufactured by Asahi Chiba) 700 g, nonylphenol 67 g instead of p- (α-cumyl) phenol, and brominated bisphenol A having reactivity with cyanenato groups as a flame retardant
Epoxy resin (ESB400, manufactured by Sumitomo Chemical) 200
g was added and dissolved by heating 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 Chemical Industry) was added to produce a resin varnish for printed wiring boards (solids concentration = 44%). However, in this resin varnish, aggregated and separated products of polystyrene resin were observed after 2 days.

Comparative Example 4 In Example 4, 1600 g of toluene, 300 g of a polyethylene resin (XM-220, manufactured by Mitsui Petrochemical) and bis (3,5-dimethyl-4-cyanatophenyl) methane (ArocyM-10, Asahi Chiba) 600g and p-
9 g of nonylphenol was added in place of (α-cumyl) phenol (manufactured by San Techno Chemical), and the mixture was stirred and dissolved. Then, 3 g of a 10% toluene solution of manganese naphthenate (Mn content = 8%, manufactured by Nippon Chemical Industry) was added and refluxed. 1 at temperature
Allowed to react for hours. Next, 150 g of tetrabromobisphenol A (Fireguard FG-2000, manufactured by Teijin Chemicals Ltd.) having reactivity with a cyanate group was added as a flame retardant, dissolved and cooled. However, since the resin solution solidified (grease-like) at around normal temperature, 1200 g of toluene was further added and dissolved by stirring, and the resin varnish for printed wiring boards (solid content =
27%).

[0050]

[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 (made 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)
Oligomers of propane (B) PCP (manufactured by San Techno Chemical); p- (α-cumyl) phenol BPA (bisphenol A, manufactured by Mitsui Toatsu Chemicals); 2,2-bis (4-hydroxyphenyl) propane NP (manufactured by Mitsui Toatsu) Nonylphenol (c) XM-220 (Mitsui Petrochemical); Polyethylene resin (d) BCL-462 (Albemarl); 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 (manufactured by Sumitomo Chemical Co., Ltd.); brominated bisphenol A type epoxy resin TBA (FG-2000, manufactured by Teijin Chemicals); brominated bisphenol A ( E) Co; 10% toluene solution of cobalt naphthenate (Co = 8%, manufactured by Nippon Chemical Industry) Zn: Zinc naphthenate (Zn = 8%, manufactured by Nippon Chemical Industry)
10% toluene solution of manganese; Mn; 10% toluene solution of manganese naphthenate (Mn = 8%, manufactured by Nippon Chemical Industry) Fe; 10% toluene solution of iron naphthenate (Fe = 5%, manufactured by Nippon Chemical Industry) Cu; naphthene Copper oxide (Cu = 5%, Nippon Chemical Industry) 10% toluene solution

The obtained resin varnish for printed wiring boards was added in an amount of 0.2
It was impregnated into an E glass cloth having a thickness of mm 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 addition, in the case of the resin varnish for printed wiring boards of Comparative Examples 1, 2 and 4, since the solid content concentration was low, the 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 the cyanate ester resin and the polyethylene resin was observed.

Next, 18 μm thick copper foils were laminated on both sides of the four prepregs, press-molded at 170 ° C. and 2.5 MPa for 60 minutes, and then heat-treated at 230 ° C. for 120 minutes to form a copper-clad laminate. Produced. 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. Table 2 shows the results.

<Characteristics Evaluation Method> Relative permittivity and dielectric loss tangent / 1 GHz: Measured by a triplate structure straight line resonator method.・ Solder heat resistance: PCT etched test piece with copper foil
(121 ° C., 0.22 MPa) and then 260
It was immersed in molten solder at 20 ° C. for 20 seconds, and its appearance was examined. "OK" in the table means that no measling and blistering occur. -Copper foil peel strength: Measured in accordance with JIS-C-6481. -Flame resistance: Measured according to the UL-94 vertical test method.

[0054]

[Table 2]

As is clear from Table 2, the laminates using the resin compositions of Examples 1 to 5 all have low relative dielectric constant and dielectric loss tangent at 1 GHz, solder heat resistance when absorbing moisture, and copper foil. Good peel strength. On the other hand, the comparative example is 1 GH
The dielectric constant and dielectric loss tangent of z are increased, and there is a problem in heat resistance and the like.

[0056]

As described above, the modified cyanate resin composition of the present invention has a low dielectric constant and a low dielectric loss tangent in a high-frequency band, has good solder heat resistance, adhesiveness and flame resistance, and has a high frequency signal. It is suitable as a resin composition for a laminate used for a printed wiring board of a device to be handled. The laminate prepreg and the metal-clad laminate of the present invention have a low dielectric loss tangent in a high-frequency band and an excellent low-loss property, and the operating frequency of wireless communication-related terminal devices, antennas and microprocessors is several hundred MHz
It is suitable for manufacturing a substrate for a printed wiring board used in a high-speed computer or the like exceeding z.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08L 23/06 C08L 23/06 H05K 1/03 610 H05K 1/03 610M F term (reference) 4F072 AA04 AA07 AB09 AB28 AD04 AD11 AE02 AE07 AF12 AF14 AF15 AF17 AF20 AG03 AH02 4J002 BB03X BC113 CG033 CM02W EB096 ED076 EG047 EG087 EU186 FD010 FD133 FD136 FD136 FD207 GF00 GQ01 4J043 PA02 QC23 SA13 SB01 TA02 UA01 ZA1 UB131 UA131 UA141

Claims (10)

[Claims] (1) A cyanate ester compound represented by the formula (1): (B) a monohydric phenol compound represented by the formula [2]: A modified cyanate ester-based curable resin for a laminate, comprising (C) a polyethylene resin, (D) a flame retardant having no reactivity with a cyanate ester compound, and (E) a metal-based reaction catalyst as essential components. Composition. 2. The method according to claim 1, wherein the modified cyanate ester resin is mixed with (B) a monohydric phenol compound in an amount of 4 to 30 parts by weight based on 100 parts by weight of the cyanate ester compound (A). A modified cyanate ester-based curable resin composition for a laminate. 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 polyethylene resin, and (D) a cyanate ester. The flame retardant having no reactivity with the compound and (E) a metal-based reaction catalyst are contained as essential components.
The modified cyanate ester-based curable resin composition for a laminate described in the above. 4. The method according to claim 1, wherein (A) the 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. 3.
4. The modified cyanate ester-based curable resin composition for a laminate according to any one of items 3 to 3. 5. The method according to claim 1, wherein (B) the monohydric phenol compound is p-
5. The modified cyanate ester-based curable resin composition for a laminate 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-.
7. A modified laminate according to claim 1, which is one kind of alicyclic flame retardant selected from (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane and hexabromocyclododecane or a mixture of two or more kinds thereof. A cyanate ester-based curable resin composition. 7. The flame retardant having no reactivity with the (D) cyanate ester compound is represented by the formula [3]: The lamination according to any one of claims 1 to 6, which is a brominated triphenylcyanurate-based flame retardant represented by the formula (1) or a mixture of at least one of these and a flame retardant having no reactivity with other cyanate ester compounds. Modified cyanate ester-based curable resin composition for boards. 8. (E) The metal-based reaction catalyst is manganese, iron,
9. The modified cyanate ester-based curable resin composition for a laminate according to claim 1, wherein the composition is one or more selected from 2-ethylhexanoate, naphthenate, and acetylacetone complex of cobalt, nickel, copper, and zinc. object. 9. A varnish obtained by dissolving or dispersing the modified cyanate ester-based curable resin composition for a laminate according to any one of claims 1 to 9 in a solvent, and impregnating the substrate with the varnish. 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 the prepregs for a laminate according to claim 10, further laminating metal foil on the upper or lower surface or one surface thereof, and heating and pressing.