JPH1121452A - Modified cyanate ester-based hardening resin composition for laminated sheet, prepreg and laminated sheet using the same composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition useful for laminated sheets good in resistance to heat and required to show low loss in a high frequency range by including a specific cyanate ester, specific monovalent phenol, polyphenylene ether resin, flame retardant unreactive with the cyanate ester, and specific catalyst. SOLUTION: This composition is obtained by including (A) 100 pts.wt. of a cyanate ester shown by formula I (R1 is CH2 or the like; and R2 and R3 are each H or the like), e.g. 2,2'-bis(4-cyanatophenyl) propane, (B) 4 to 30 pts.wt. of a monovalent phenol shown by formula II (R4 and R5 are each H or the like), (C) 5 to 30 pts.wt. of a polyphenylene ether resin, (D) 5 to 30 pts.wt., per 100 pts.wt. of the components A, B and C, of a flame retardant unreactive with the cyanate ester above, and (E) 1 to 300 wt. ppm, per gram of the component A, of a metal-based reaction catalyst (e.g. a complex of manganese).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified cyanate ester-based curable resin composition for a laminate, which is suitable for producing a laminate requiring low loss in a high frequency band, and a prepreg for a laminate using the same. And a metal-clad laminate.

[0002]

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.

[0003] The transmission loss in a printed wiring board is determined 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 with operating frequencies exceeding 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 increase in the signal frequency as described above, a composition made of 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.

[0006] In order to improve high-frequency characteristics by using a thermoplastic resin, a polyphenylene ether resin (PPO or PP) disclosed in Japanese Patent Publication No. 5-77705 has been proposed.
E) and a resin composition of a crosslinkable polymer / monomer, and a resin composition of a polyphenylene ether resin having a specific curable functional group and a crosslinkable monomer as disclosed in JP-B-6-92533. Among the heat-resistant thermoplastic resins, there is a method using a polyphenylene ether-based resin composition having good dielectric properties.

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

[0008]

[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.

[0009] 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 since the resin composition is mainly composed of a polyphenylene ether resin which is originally a thermoplastic polymer. Was. 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.

JP-B-63-33506 and JP-A-5-33506
In the method disclosed in Japanese Patent No. 310771, the thermosetting resin used in combination with the polyphenylene ether resin is a bismaleimide / cyanate ester resin or a phenol-modified resin / cyanate ester reactant. There was a problem that it was still insufficient. In addition, when the compounding amount of the polyphenylene ether resin is increased in order to improve the high frequency characteristics, the melt viscosity of the resin composition becomes high similarly to the above-mentioned polyphenylene ether-based resin composition, and the fluidity is insufficient, so that the moldability is poor. There was a problem.

A resin composition obtained by kneading a polyphenylene ether resin and a cyanate ester resin as disclosed in JP-B-61-18937 has good dielectric properties and, when modified with a cyanate ester resin, has a low melt viscosity. Although the moldability of the composition is relatively good, when a cyanate ester is used alone as a curable component, the dielectric properties of the cured resin tend to have a higher dielectric loss tangent than the value of the dielectric constant. However, there is a problem that the transmission loss cannot be sufficiently reduced. Further, when the compounding amount of the cyanate ester is reduced (the compounding amount of the polyphenylene ether resin is increased) in order to lower the dielectric loss tangent, the melt viscosity of the resin composition increases as in the case of the above-mentioned polyphenylene ether-based resin composition, and the fluidity becomes low. There was a problem that formability was poor due to lack.

In view of such a situation, 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.

[0014]

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

[0015]

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[0016]

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Still further, the present invention provides a method of formula (A), wherein
When a modified cyanate ester resin obtained by reacting 4 to 30 parts by weight of (B) a monohydric phenol compound represented by the formula (2) with 100 parts by weight of the cyanate ester compound represented by It is preferred.

[0018]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Dielectric properties such as polymer materials are greatly affected by the orientation polarization of dipoles. Therefore, by reducing the number of polar groups in the molecule, the dielectric constant can be reduced, and the mobility of polar groups can be suppressed. Thereby, the dielectric loss tangent 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 more 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) By blending a monohydric phenol compound in an appropriate amount, a cyanato group remaining as unreacted is converted into imide carbonate to reduce its polarity, thereby lowering the dielectric constant and dielectric loss tangent of the cured product. 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, phenol compounds such as nonylphenol have been used as co-catalysts 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 modified cyanate ester-based curable resin composition for a laminate of the present invention, the amount of the monohydric phenol compound is important. In other words, if the amount is small, it is not possible to react with all the cyanato groups remaining as unreacted to lower the polarity, and if the amount is more than the required amount, it itself remains unreacted and its own remains. This is because the polarity of the hydroxyl group deteriorates the dielectric properties of the cured product.

Further, in the modified cyanate ester-based curable resin composition for a laminate according to the present invention, the dielectric properties can be obtained by blending (C) polyphenylene ether resin, which is a thermoplastic resin having good dielectric properties, with the above-mentioned modified cyanate ester resin. The characteristics are improved. The cyanate ester resin and the polyphenylene ether 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 the ( B) When the reaction of the monohydric phenol compound is carried out in a solvent solution of polyphenylene ether resin, a so-called “semi-IPN (interpenetrating polymer netwo
It was found that an rk) -modified 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. It is essential that such flame retardants include alicyclic flame retardants (aliphatic ring-type flame retardants), and these are hydrocarbon-based low-polar compounds, which deteriorate the dielectric properties of the cured product. Less is. 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.

The modified cyanate ester-based curable resin composition for a laminate of the present invention comprises (A) a cyanate ester compound represented by the formula (1) and (B) a cyanate ester compound represented by the formula (2).
The essential components are a phenolic compound, a (C) polyphenylene ether resin, (D) a flame retardant having no reactivity with the cyanate ester compound, 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, 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 dicyclopentadiene polymer. Among them, 2,2-bis (4
-Cyanatophenyl) propane and 2,2-bis (3,
Any one of 5-dimethyl-4-cyanatophenyl) methane or a mixture of both is preferable because the balance between the dielectric properties of the cured product and the moldability is particularly good. Also (A)
As the cyanate ester compounds, one kind may be used alone, or two or more kinds 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. 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 the (B) 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 more preferably 5 to 2 parts by weight with respect to 00 parts by weight.
More preferably, it is 5 parts by weight. If the 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 (A) cyanate ester compound and (B) the monohydric phenol compound in the present invention are generally 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) A modified cyanate ester resin may be prepared by charging the monohydric phenolic compound from the initial stage of the reaction and then reacting by adding all of the above proper amount, or a part of the above proper amount may be reacted 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.

The polyphenylene ether resin (C) in the present invention includes, for example, poly (2,6-dimethyl-
Alloyed polymer of 1,4-phenylene) ether, poly (2,6-dimethyl-1,4-phenylene) ether and polystyrene, poly (2,6-dimethyl-1,4-phenylene) ether and styrene-butadiene copolymer And the like. Among them, poly (2,6)
-Dimethyl-1,4-phenylene) ether and polystyrene alloy and poly (2,6-dimethyl-)
Alloyed polymers of 1,4-phenylene) ether and styrene-butadiene copolymer are preferred, and poly (2,6)
-Dimethyl-1,4-phenylene) ether component in 50
It is preferable that the polymer is contained in an amount of not less than 65% by weight because the dielectric properties of the cured product are good.

In the present invention, the compounding amount of the polyphenylene ether resin (C) is preferably 5 to 300 parts by weight, more preferably 10 to 200 parts by weight, based on 100 parts by weight of the cyanate ester compound (A). And more preferably 15 to 100 parts by weight. If the compounding amount of the (C) polyphenylene ether resin is less than 5 parts by weight, sufficient dielectric properties 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. Worse and again (A)
The reactivity of cyanate esters also tends to be poor.

The flame retardant having no reactivity with the cyanate ester compound (D) in the present invention includes, for example,
1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclohexane, hexabromocyclododecane, polybromodiphenyl ether,
Brominated polystyrene, brominated polycarbonate, brominated triphenyl cyanate-based flame retardant represented by the formula (3), and the like, among which 1,2-dibromo-4-
(1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane,
2,4,6-tris (tribromophenoxy) -1,
It is more preferable because the cured product from which 3,5-triazine or the like is obtained has good dielectric properties.

[0034]

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In the present invention, the compounding amount of the flame retardant having no reactivity with the cyanate ester compound (D) is (A)
Total amount of cyanate ester compound, (B) monohydric phenol compound and (C) polyphenylene ether resin is 1
The amount is preferably 5 to 30 parts by weight, more preferably 5 to 20 parts by weight, and more preferably 10 to 100 parts by weight.
More preferably, it is 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-based 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 preferably 1 to 300 ppm, and more preferably 1 to 300 ppm based on 1 (g) of the cyanate ester compound (A).
More preferably, the concentration is set to 00 ppm.
m is more preferable. (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 addition, the compounding time of the metal-based reaction catalyst (E) in the present invention may be such that the amounts required as a reaction accelerator and a curing accelerator in producing the modified cyanate ester-based curable resin composition are simultaneously combined. When using a modified cyanate ester-based curable resin composition, the amount necessary for promoting the modification reaction is used, and after the reaction is completed, the remaining catalyst or another metal-based catalyst is added and mixed as a curing accelerator. Is also good.

The modified cyanate ester-based curable resin composition for a laminated board of the present invention may contain, if necessary, an inorganic filler and other additives in addition to the above essential components. As fillers, silica, alumina, aluminum hydroxide, calcium carbonate, clay, talc, silicon nitride,
Boron nitride, titanium oxide, barium titanate, lead titanate, strontium titanate and the like can be used. The compounding amount may be set to 1
For 250 parts by weight or less with respect to 00 parts by weight,
When the resin varnish of the present invention is impregnated into a substrate such as a glass cloth, it is preferable because a uniform amount of the resin adhered and a good appearance can be obtained.

The above-described modified cyanate ester-based curable resin composition for a laminate according to the present invention is used, for example, for producing a prepreg for a laminate or a metal-clad laminate as shown below. That is, first, a prepreg is prepared by dissolving or dispersing the modified cyanate ester-based curable resin composition for a laminate in a solvent into a varnish, impregnating a substrate such as a glass cloth, and drying. Then, one or an arbitrary 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 the modified cyanate ester-based curable resin composition for a laminate of the present invention is varnished include aromatic hydrocarbons such as benzene, toluene and xylene, trichloroethylene, chlorobenzene and the like. Halogenated hydrocarbons, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, and nitrogen solvents such as N-methylpyrrolidone. 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 from 150 to 50 parts by weight based on 100 parts by weight of the polyphenylene ether resin (C).
0 parts by weight is preferable, 150 to 400 parts by weight is more preferable, and 150 to 300 parts by weight is further preferable.

Further, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone have low solubility in the modified cyanate ester-based curable resin composition for a laminate of the present invention, but when used in combination with the above-mentioned solvents, the ketones may become less soluble. Producing a suspension solution of the resin composition of the invention,
There is an advantage that a solution having a high concentration and a low viscosity can be obtained. From this viewpoint, as a solvent used when varnishing the modified cyanate ester-based curable resin composition for a laminate of the present invention, aromatic hydrocarbons such as benzene, toluene, xylene and acetone, methyl ethyl ketone, methyl isobutyl ketone And mixed solvents with ketones such as cyclohexanone are particularly preferred. The amount of the ketone solvent is 50 to 500 parts by weight per 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, even more preferably 50 to 300 parts by weight.

[0042]

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 (C) a polyphenylene ether resin, PKN4752 (manufactured by Nippon GE Plastics Co., Ltd.), were placed in a 5-liter four-neck separable flask equipped with a thermometer, a cooling pipe, and a stirrer. (Trade name) 210 g was charged and heated to 80 ° C. to dissolve with stirring. Next, as the cyanate ester compound (A), 2,2-bis (4-cyanatephenyl) propane (ArocyB-10, trade name, manufactured by Asahi Ciba Co., Ltd.) 7
00g and (B) a monohydric phenol compound as p-
64 g of (α-cumyl) phenol (manufactured by San Techno Chemical Co., Ltd.), (D) brominated triphenylcyanurate (Piroguard SR-245, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as a flame retardant having no reactivity with cyanate ester compounds After charging and dissolving 135 g, cobalt naphthenate (Co content = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.)
4 g of a 10% by weight toluene solution 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% by weight toluene solution of zinc naphthenate (Zn content = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) was added and dissolved by stirring, followed by resin varnish for laminate (solids concentration = 51
% By weight).

Example 2 300 g of toluene and a polyphenylene ether resin (PKN4) were placed in a 5-liter four-neck separable flask equipped with a thermometer, a condenser, and a stirrer.
752, 140 g (trade name, manufactured by Nippon GE Plastics Co., Ltd.), and the mixture was heated to 80 ° C. and dissolved by stirring.
Next, 2,2-bis (4-cyanatephenyl) propane (ArocyB-10, trade name, manufactured by Asahi Ciba Co., Ltd.) 70
0 g, 10 g of p- (α-cumyl) phenol (manufactured by San Techno Chemical Co., Ltd.) and 125 g of brominated triphenylcyanurate (Pyroguard SR-245, trade name of Daiichi Kogyo Seiyaku Co., Ltd.) were added, dissolved, and then manganese naphthenate was dissolved. 3 g of a 10% by weight toluene solution of (Mn content = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) 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 1 g of a 10% by weight toluene solution of zinc naphthenate (Zn content = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) were added and dissolved by stirring. A resin varnish for a laminate (solid content concentration: 54% by weight) was produced.

Example 3 300 g of toluene and polyphenylene ether (PKN475) were placed in a 5-liter four-neck separable flask equipped with a thermometer, a condenser, and a stirrer.
2. Nippon GE Plastics Co., Ltd. product name) 8
After charging 0 g, the mixture was heated to 80 ° C. and dissolved by stirring. Then α,
800 g of α'-bis (4-cyanatophenyl) -m-diisopropylbenzene (RTX-366, trade name of Asahi Ciba Co., Ltd.) and 10 g of p- (α-cumyl) phenol (San Techno Chemical Co., Ltd.) are introduced and dissolved. Thereafter, 2 g of a 10% by weight toluene solution of iron naphthenate (iron content = 5% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) was added, and reacted at reflux temperature for 1 hour. Then, tetrabromocyclooctane (Saytex BC-48, albemarle) was added. Brand name)
110 g was introduced and dissolved. The reaction solution was cooled and the internal temperature was 9
When the temperature reaches 0 ° C, methyl ethyl ketone (MEK) 600g
Was added with stirring to suspend. After further cooling to room temperature, 75 g of p- (α-cumyl) phenol and 2 g of a 10% by weight toluene solution of copper naphthenate (copper content = 5% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) were added and dissolved by stirring. A resin varnish for a laminate (solid content concentration: 54% by weight) was produced.

Example 4 600 g of toluene and a polyphenylene ether resin (PKN4) were placed in a 5-liter four-neck separable flask equipped with a thermometer, a condenser, and a stirrer.
752, 300 g (trade name, manufactured by Nippon GE Plastics Co., Ltd.) were charged, heated to 80 ° C., and dissolved by stirring.
Next, bis (3,5-dimethyl-4-cyanatophenyl)
After adding and dissolving 600 g of methane (ArocyM-10, trade name of Asahi Ciba Co., Ltd.) and 30 g of p- (α-cumyl) phenol (manufactured by San Techno Chemical Co.), cobalt naphthenate (Co content = 8% by weight, Japan) 4 g of a 10% by weight toluene solution of Chemical Industry Co., Ltd. was added and reacted at reflux temperature for 1 hour, and then hexabromocyclododecane (CD-75P, trade name of Great Lakes Co.) 1
50 g was introduced and dissolved. The reaction solution was cooled and the internal temperature was 90
When the temperature reached ° C, 750 g of methyl ethyl ketone (MEK) was added with stirring to suspend. After further cooling to room temperature, 120 g of p- (α-cumyl) phenol was added and dissolved by stirring to obtain a resin varnish for a laminate (solids concentration = 47%).
% By weight).

Example 5 750 g of toluene and a polyphenylene ether resin (PKN4) were placed in a 5-liter four-neck separable flask equipped with a thermometer, a condenser, and a stirrer.
752, 400 g (trade name, manufactured by Nippon GE Plastics Co., Ltd.), and the mixture was heated to 80 ° C. and dissolved by stirring.
Next, 2,2-bis (4-cyanatophenyl) -1,1,1
1,3,3,3-hexafluoropropane (Arocy
F-10, trade name, manufactured by Asahi Ciba Corporation) 500 g, p-
(Α-cumyl) phenol (manufactured by San Techno Chemical)
After charging and dissolving 28 g, 6 g of a 10% by weight toluene solution of copper naphthenate (Cu content = 5% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) was added and reacted at reflux temperature for 1 hour. 150 g of 4- (1,2-dibromoethyl) cyclohexane (Saytex BCL-462, trade name of Albemarle Co.) was charged and dissolved. Then, the reaction solution was cooled, and when the internal temperature reached 90 ° C., 500 g of methyl ethyl ketone (MEK) was added with stirring to suspend the mixture. After cooling to room temperature, manganese naphthenate (Mn
1 g of a 10% by weight toluene solution containing 8% by weight (manufactured by Nippon Chemical Industry Co., Ltd.) was added and dissolved by stirring to prepare a resin varnish for a laminate (solids concentration = 46% by weight).

Comparative Example 1 In Example 1, 1800 g of toluene was added to a polyphenylene ether resin (PKN47).
52, product name of Japan GE Plastics Co., Ltd.)
210 g, 2,2-bis (4-cyanatephenyl) propane (ArocyB-10, trade name, manufactured by Asahi Ciba Co., Ltd.) 700 g and 2,2-bis (4-hydroxyphenyl) in place of p- (α-cumyl) phenol ) 69 g of propane (BPA; bisphenol A, manufactured by Mitsui Toatsu Chemicals Co., Ltd.) is added, and after stirring and dissolving, a 10% by weight toluene dilute solution of cobalt naphthenate (Co content = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) 3 g was added and reacted at reflux temperature for 1 hour. Next, a brominated bisphenol A type epoxy resin (ESB400, trade name, manufactured by Sumitomo Chemical Co., Ltd.) having a reactivity with a cyanato group as a flame retardant 20
0 g was introduced, dissolved and cooled. However, since the resin solution was solidified (grease-like) at around normal temperature, 1200 g of toluene was further added and dissolved by stirring to produce a resin varnish for a laminate (solids concentration = 28% by weight).

Comparative Example 2 In Example 1, 1800 g of toluene was added to a polyphenylene ether resin (PKN47).
52, product name of Japan GE Plastics Co., Ltd.)
Nonylphenol (manufactured by Mitsui Toatsu Chemicals, Inc.) instead of 210 g, 700 g of 2,2-bis (4-cyanatephenyl) propane (ArocyB-10, trade name, manufactured by Asahi Chiba Co., Ltd.) and p- (α-cumyl) phenol 11
g, and after stirring and dissolving, 10% by weight of cobalt naphthenate (Co content = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.)
4 g of a diluted toluene solution was added and reacted at a 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, trade name, manufactured by Sumitomo Chemical Co., Ltd.) was added and dissolved, and cooled. However, since the resin solution was solidified (grease-like) at around normal temperature, 900 g of toluene was further added and dissolved by stirring to produce a resin varnish for a laminate (solid content = 29% by weight).

Comparative Example 3 In Example 1, 1500 g of toluene was added to a polyphenylene ether resin (PKN47).
52, product name of Japan GE Plastics Co., Ltd.)
210 g was added, heated to 80 ° C., and dissolved by stirring. Then, 2,2-bis (4-cyanatephenyl) propane (A
Instead of rocyB-10 (trade name, manufactured by Asahi Ciba Co., Ltd.), 700 g of an oligomer of 2,2-bis (4-cyanatephenyl) propane (ArocyB-30, trade name, manufactured by Asahi Ciba Co., Ltd.), p- (α-cumyl) ) In place of phenol, 67 g of nonylphenol and 200 g of a brominated bisphenol A-type epoxy resin (ESB400, manufactured by Sumitomo Chemical Co., Ltd.) having a reactivity with a cyanato group as a flame retardant were added and dissolved by heating at 80 ° C. for 1 hour. Then, the mixture was cooled to room temperature, and 2 g of a 10% by weight toluene solution of zinc naphthenate (Zn content = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) was added, and a resin varnish for a laminate (solids concentration = 44% by weight) was added. Was manufactured. However, in this resin varnish, after 2 days, a coagulated and separated product of the polyphenylene ether resin was observed.

Comparative Example 4 In Example 4, 1600 g of toluene and polyphenylene ether resin (PKN47) were used.
52, product name of Japan GE Plastics Co., Ltd.)
Instead of 300 g, 600 g of bis (3,5-dimethyl-4-cyanatophenyl) methane (ArocyM-10, trade name, manufactured by Asahi Ciba Co., Ltd.) and p- (α-cumyl) phenol (manufactured by San Techno Chemical Co., Ltd.) 9 g of nonylphenol was added, and after stirring and dissolving, 3 g of a 10% by weight toluene solution of manganese naphthenate (Mn content = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) was added and reacted at reflux temperature for 1 hour. Then, tetrabromobisphenol A (Fireguard FG-2000, trade name, manufactured by Teijin Chemicals Limited) having a reactivity with a cyanato group as a flame retardant 15
0 g was introduced, dissolved and cooled. However, since the resin solution was solidified (grease-like) at around normal temperature, 1200 g of toluene was further added and dissolved by stirring to produce a resin varnish for a laminate (solid content = 27% by weight).

[0052]

[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 Chiba Corporation); 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane RTX-366 (Asahi Α, α'-bis (4-cyanatophenyl) -m-diisopropylbenzene B-30 (manufactured by Asahi Ciba); an oligomer of 2,2-bis (4-cyanatophenyl) propane (B) PCP (manufactured by San Techno Chemical Co., Ltd.); p- (α
-Cumyl) phenol BPA (bisphenol A, manufactured by Mitsui Toatsu Chemicals, Inc.);
2,2-bis (4-hydroxyphenyl) propane NP (manufactured by Mitsui Toatsu Chemicals, Inc.); nonylphenol (C) PPO (nonyl PKN4752, trade name, manufactured by Nippon CIE Plastics Co., Ltd.); polyphenylene ether (D) BCL- 462 (trade name of Albemarle); 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane BC-48 (trade name of Albemarle); tetrabromocyclooctane CD-75P (trade name of Great Lakes) Hexabromocyclododecane SR-245 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.); 2,4,6-
Tris (tribromophenoxy) -1,3,5-triazine ESB-400 (trade name, manufactured by Sumitomo Chemical Co., Ltd.); brominated bisphenol A type epoxy resin TBA (FG-2000, trade name, manufactured by Teijin Chemicals Limited);
Brominated bisphenol A (E) Co; 10% by weight toluene solution of cobalt naphthenate (Co = 8% by weight, manufactured by Nippon Chemical Industry) Zn; 10% by weight toluene solution Mn; 10% by weight toluene solution of manganese naphthenate (Mn = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) 10% by weight toluene solution Cu; 10% by weight toluene solution of copper naphthenate (Cu = 5% by weight, manufactured by Nippon Chemical Industry Co., Ltd.)

The obtained resin varnish for a laminate was 0.2 mm
Impregnated into a thick E glass cloth (basis weight 209 g / m ² )
Heating was performed at 0 ° C. for 5 to 10 minutes (so that the gel time (170 ° C.) becomes 5 to 7 minutes) to obtain a prepreg for a laminate having a resin adhesion amount of 40 to 45% by weight. Comparative Examples 1, 2 and 4
In the case of the resin varnish for laminates, since the solid content concentration is low, the above impregnation coating operation was repeated twice to obtain a resin adhesion amount of 40.
A prepreg for a laminate of about 45% by weight was obtained. In the prepreg of Comparative Example 3, separation of the cyanate ester resin and the polyphenylene ether resin was observed.

Next, four prepregs and 18 μm-thick copper foil were laminated on both sides, press-formed at 170 ° C. and 2.5 MPa for 60 minutes, and heat-treated at 230 ° C. for 120 minutes to form a copper foil-clad laminate. Was prepared. In the obtained copper foil clad laminate,
Then, dielectric properties, solder heat resistance, copper foil peeling strength and flame resistance were measured 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: The test piece from which the copper foil was removed by etching was held in PCT (121 ° C., 0.22 MPa), then immersed in molten solder at 260 ° C. for 20 seconds, and the appearance was examined. “OK” in the table indicates that no measling and blistering occurred, and “NG” indicates that measling and blistering occurred. -Copper foil peel strength: Measured according to JIS-C-6481. -Flame resistance: Measured according to the UL-94 vertical test method.

[0057]

[Table 2]

As is clear from Table 2, the laminates using the modified cyanate ester-based curable resin compositions for laminates of Examples 1 to 5 all have low relative dielectric constant and dielectric loss tangent at 1 GHz. Good soldering heat resistance at the time of moisture absorption and good copper foil peeling strength. On the other hand, the comparative example has a high relative dielectric constant and dielectric loss tangent of 1 GHz, and is inferior in heat resistance and the like.

[0059]

EFFECT OF THE INVENTION The modified cyanate-based curable resin composition for laminates of the present invention, the prepreg for laminates and the metal-clad laminates using the same, have a low dielectric constant and a low dielectric loss tangent in a high frequency band, and have a low heat resistance. It has good properties, copper foil peeling strength and flame resistance, and is suitable as a resin composition for laminates used for laminates of equipment that handles high-frequency signals. The varnish used for the prepreg for a laminate can be highly concentrated, and a desired solid content can be obtained by one coating like a conventional epoxy resin varnish. In addition, the metal-clad laminate of the present invention has a low dielectric loss tangent in a high-frequency band and excellent low-loss properties, and is suitable for wireless communication-related terminal equipment, antennas, and high-speed computers in which the operating frequency of a microprocessor exceeds several hundred MHz. It is suitable as a substrate for a wiring board to be used.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5/3477 C08K 5/3477 C09D 179/00 C09D 179/00 H05K 1/03 610 H05K 1/03 610H 610S // C07D 251 / 34 C07D 251/34 N C08J 5/24 CEZ C08J 5/24 CEZ (C08L 79/00 71:12) (72) Inventor Harumi Negishi 1500 Oji Ogawa, Shimodate City, Ibaraki Pref. Hitachi Chemical Co., Ltd. Shimodate Plant

Claims (12)

[Claims] (A) a cyanate ester compound represented by the formula (1), (B) a monohydric phenol compound represented by the formula (2), (C) a polyphenylene ether resin,
A modified cyanate ester-based curable resin composition for a laminate, comprising (D) a flame retardant having no reactivity with a cyanate ester compound and (E) a metal-based reaction catalyst as essential components. Embedded image Embedded image 2. The modified cyanate ester resin comprises (A)
For 100 parts by weight of the cyanate ester compound,
The modified cyanate ester-based curable resin composition for a laminate according to claim 1, wherein (B) a monohydric phenol compound is blended in an amount of 4 to 30 parts by weight. 3. A modified cyanate ester resin obtained by reacting (A) a cyanate ester compound with (B) a part or all of a monohydric phenol compound, (C) a polyphenylene ether resin, and (D) a cyanate ester The modified cyanate ester-based curable resin composition for a laminate according to claim 1 or 2, comprising a flame retardant having no reactivity with the class compound and (E) a metal-based reaction catalyst as essential components. Stuff. 4. A cyanate ester compound (A)
(B) monohydric phenolic compounds 4 to 3 with respect to 0 parts by weight.
0 parts by weight, (C) 5 to 30 polyphenylene ether resin
0 parts by weight, (E) 1 to 300 ppm of the metal-based reaction catalyst based on the cyanate ester compound 1, and 100 parts by weight of the total of the above (A), (B) and (C)
The modified cyanate ester-based curable composition for a laminate according to any one of claims 1 to 3, further comprising (D) 5 to 30 parts by weight of a flame retardant not reactive with the cyanate ester compound. Resin composition. 5. The method according to claim 1, wherein (A) the cyanate ester compound is
4. The method according to claim 1, wherein the compound is any one of 2,2-bis (4-cyanatophenyl) propane and 2,2-bis (3,5-dimethyl-4-cyanatophenyl) methane or a mixture of both. 5. The modified cyanate ester-based curable resin composition for a laminate according to any one of 4. 6. The method of claim 1, wherein (B) the monohydric phenol compound is p-
The modified cyanate ester-based curable resin composition for a laminate according to any one of claims 1 to 5, which is (α-cumyl) phenol. 7. The polyphenylene ether resin (C),
An alloyed polymer of poly (2,6-dimethyl-1,4-phenylene) ether and polystyrene or styrene-butadiene copolymer, comprising poly (2,6-dimethyl-
The modified cyanate ester-based curable resin composition for a laminate according to any one of claims 1 to 6, comprising at least 50% by weight of (1,4-phenylene) ether. 8. The flame retardant having no reactivity with (D) a cyanate ester compound, wherein the flame retardant is 1,2-dibromo-4-
8. An alicyclic flame retardant selected from (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane and hexabromocyclododecane, or a mixture of two or more alicyclic flame retardants. A modified cyanate ester-based curable resin composition for a laminate. 9. The flame retardant having no reactivity with the cyanate ester compound (D) is a brominated triphenyl cyanurate flame retardant represented by the formula (3) or at least one of these and other cyanate esters. The modified cyanate ester-based curable resin composition for a laminate according to any one of claims 1 to 8, which is a mixture of two or more kinds of a compound and a non-reactive flame retardant. Embedded image (E) The metal-based reaction catalyst is manganese,
The laminate according to any one of claims 1 to 9, wherein the laminate is one or more selected from 2-ethylhexanoate, naphthenate, and acetylacetone complex of iron, cobalt, nickel, copper, and zinc. A modified cyanate ester-based curable resin composition. 11. 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 10 in a solvent, and impregnating the substrate with the varnish. A prepreg for a laminate obtained by drying at 80 to 200 ° C. 12. A metal-clad laminate obtained by laminating one or more laminate prepregs according to claim 11, further laminating metal foil on the upper or lower surface or one surface thereof, and heating and pressing.