KR100835785B1 - Resine composition for printed circuit board and composite substrate and copper laminates using the same - Google Patents

Abstract

A resin composition for a printed circuit board is provided to realize excellent moldability and processability, to improve dielectric property, heat resistance and adhesion strength, and to obtain a copper clad laminate having a low dielectric constant suitable for high-speed signaling. A resin composition for a printed circuit board comprises: (a) a modified polyphenylene ether resin obtained through the redistribution reaction of polyphenylene ether in the presence of 9,10-dihydro-9-oxa-10-(dihydroxyaryl)-10- phosphaphenanthrene-10-oxide; (b) a dicyclopentadiene epoxy resin represented by the following formula 1; and (c) an alkylphenol aldehyde novolac curing agent represented by the following formula 2. In formula 1, m is an integer of 0 or greater. In formula 2, R1 is a C1-C12 alkyl, C1-C6 alkyl, C5-C7 cycloalkyl or C6-C24 aromatic hydrocarbon group; R2 is H or a C1-C12 alkyl; n is an integer of 0 or greater.

Description

RESINE COMPOSITION FOR PRINTED CIRCUIT BOARD AND COMPOSITE SUBSTRATE AND COPPER LAMINATES USING THE SAME}

The present invention relates to a resin composition for producing a printed circuit board (PCB) having excellent dielectric properties, a composite substrate and copper foil laminate using the same.

As such a printed circuit board, conventionally, a laminated board manufactured by heating and press molding a prepreg obtained by impregnating and drying an epoxy resin or polyimide on a substrate such as glass fiber cloth and drying a predetermined number of sheets has been used. However, with the recent miniaturization and high performance of electronic devices, high density and multi-layered printed circuit boards are rapidly progressing, and thus, prepreps obtained by impregnating and drying epoxy resin or polyimide on a substrate such as glass fiber cloth as an insulating substrate of such a printed circuit board. The copper-clad laminated board manufactured by heating and press-molding after overlapping predetermined number of legs is used.

On the other hand, since electronic information devices such as computers process a large amount of information in a short time, there is a problem that transmission loss increases and signal delay time increases as the operating frequency increases, and to solve this problem, low dielectric properties and low dielectric tangent There is a need for a copper foil laminate having a (tanδ) property. In general, since a signal delay time in a printed circuit board is increased in proportion to the square root of the relative dielectric constant? Of the insulator around the wiring, a resin composition having a low dielectric constant is required for a substrate requiring a high transfer rate. However, even in the case of FR-4 grade copper foil laminates which are commonly used at present, they exhibit relatively large dielectric constants of about 4.5 to 5.5, which causes problems in transmission loss and signal delay time.

As a conventional resin composition that copes with the high frequency of the signal as described above and improves the high frequency characteristics of a printed circuit board, a method of using a cyanate ester having a very low dielectric constant among thermosetting resins in combination with an epoxy resin is also known. The method of using phosphorus fluororesin, polyphenylene ether resin, etc. is known.

In this technique, however, the high dielectric constant of the epoxy resin, which is the basis thereof, has not only a high frequency characteristic, but also increases the ratio of cyanate ester resin or thermoplastic resin used to lower the dielectric constant. In the process of manufacturing the serious problem that the workability or workability is greatly reduced. In particular, when the polyphenylene ether resin, which is a thermoplastic resin, has a problem in that the melt viscosity of the resin composition is increased and fluidity is greatly reduced, the grooves between the fine circuit patterns or in the process of manufacturing the laminate by press molding at high temperature and high pressure. In the process of manufacturing a multilayer printed wiring board that needs to be filled, there is a great difficulty, and also has a problem that the adhesive strength and heat resistance with copper foil is greatly reduced.

On the other hand, the conventional method of manufacturing the laminated board which improved the dielectric characteristic, heat resistance, and moisture resistance using the resin composition which mix | blended the phenol addition butadiene polymer with the epoxy resin is also known. However, due to the high molecular weight of the phenol-added butadiene polymer, when the sheet-like substrate is impregnated and dried to produce a prepreg, bubbles are severely generated on the surface of the prepreg, and as a result, voids are generated in the molded laminate, thereby insulating the printed circuit board As a result, a serious problem arises that the use thereof is inappropriate.

On the other hand, focusing on the very high dielectric constant of E-glass used as a base material in conventional FR-4 copper clad laminates, the synthetic polyamide fiber having low dielectric constant is used as the base material or D-glass or quartz. Examples have been reported, but in this case there is a problem that the wear of the drill is severe when drilling the printed board, and above all, the manufacturing cost of the printed board is increased.

In order to solve such a technical problem, the present invention can not only eliminate voids due to foaming on the surface of the prepreg in the laminate by excellent moldability and workability, but also have properties such as dielectric properties, heat resistance, and adhesive strength. An object of the present invention is to provide a resin composition for a printed circuit board which can be greatly improved.

Moreover, an object of this invention is to provide the composite base material and copper foil laminated board which used the said resin composition.

The present invention relates to (a) polyphenylene ether with 9,10-dihydro-9-oxa-10- (dihydroxyaryl) -10-phosphaphenanthrene 10-oxide (9,10-dihydro-9-oxa Polyphenylene ether resin modified by redistribution in the presence of -10- (dihydroxyaryl) -10-phosphaphenanthrene 10-oxide);

(b) a dicyclopentadiene epoxy resin of formula (1); And

(c) It provides a resin composition for a printed circuit board comprising an alkylphenol aldehyde novolac curing agent of the formula (2).

[Formula 1]

In formula 1, m is an integer of 0 or more;

[Formula 2]

In formula (2), R ¹ is a C ₁ to C ₁₂ alkyl group, C ₁ to C ₆ alkyl group, C ₅ to C ₇ cycloalkyl group, or C ₆ to C ₂₄ aromatic hydrocarbon group; R ² is hydrogen or an alkyl group of C ₁ to C ₁₂ ; n is an integer of 0 or more.

In another aspect, the present invention provides a composite substrate formed by coating or impregnating the resin composition on a substrate and then drying.

In addition, the present invention provides a copper foil laminated plate formed by laminating the composite substrate and copper foil and forming a heat-pressing molding.

Hereinafter, the present invention will be described in detail.

The resin composition for a printed circuit board of the present invention is redistributed to a polyphenylene ether in the presence of 9,10-dihydro-9-oxa-10- (dihydroxyaryl) -10-phosphaphenanthrene 10-oxide. It is characterized by including a modified polyphenylene ether resin. Specifically, the high molecular weight polyphenylene ether and 9,10-dihydro-9-oxa-10- (dihydroxyaryl) -10-phosphaphenanthrene 10-oxide compound are redistributed and modified to low molecular weight. It contains polyphenylene ether resin.

Conventionally, when a high molecular weight polyphenylene ether is modified with a low molecular weight polyphenylene ether resin, a compound such as a phenol derivative or bisphenol A is generally used. In this case, rotation is possible due to molecular structure, resulting in a decrease in dielectric constant. .

However, in the present invention, high-molecular-weight poly is obtained by using 9,10-dihydro-9-oxa-10- (dihydroxyaryl) -10-phosphaphenanthrene 10-oxide instead of a phenol derivative or bisphenol A that is conventionally used. By modifying phenylene ether with a low molecular weight polyphenylene ether resin, the molecular structure prevents rotation and introduces a large number of hydrophobic, bicyclic hydrocarbon groups, thereby reducing the electron polarization and reducing the dielectric constant. In addition, 9,10-dihydro-9-oxa-10- (dihydroxyaryl) -10-phosphaphenanthrene 10-oxide has a bulky molecular structure and a high degree of crystallinity compared to conventional phenol derivatives and bisphenol A. Because of the high molecular weight modified polyphenylene ether resin can be improved in the properties of the glass transition temperature. In addition, it is possible to realize a low dielectric and low loss of the substrate through the improvement of the dielectric properties, it is possible to enhance the hygroscopic properties due to the increase in hydrophobic groups. In addition, crosslinking properties can be enhanced to enhance thermal and chemical resistance properties.

Therefore, the composite base material and the copper foil laminated plate manufactured using the resin composition of the present invention has the advantage of improving the physical properties such as formability, processability, dielectric properties, heat resistance, adhesive strength.

In addition, since 9,10-dihydro-9-oxa-10- (dihydroxyaryl) -10-phosphaphenanthrene 10-oxide is self-extinguishing due to the phosphorus (P) component contained in the molecule, Including modified polyphenylene ether resin may have a flame retardant properties. Therefore, the composite base material and the copper foil laminated plate manufactured using the resin composition of the present invention that does not include a separate flame retardant material may have excellent flame retardant properties.

In the resin composition for a printed circuit board of the present invention, the polyphenylene ether is 10 to 60 parts by weight; The 9,10-dihydro-9-oxa-10- (dihydroxyaryl) -10-phosphaphenanthrene 10-oxide is 0.1 to 5 parts by weight; The dicyclopentadiene epoxy resin is 10 to 40 parts by weight; And 10 to 40 parts by weight of the alkylphenol aldehyde novolac curing agent.

In the present invention, a high molecular weight polyphenylene ether can be used as the polyphenylene ether to be modified, and a number average molecular weight of 1000 to 30000 can be used. In addition, if polyphenylene ether is a main skeleton, it will not specifically limit.

In addition, the 9,10-dihydro-9-oxa-10- (dihydroxyaryl) -10-phosphaphenanthrene 10-oxide is one selected from the group consisting of a compound of formula 3 and a compound of formula 4 The above compound may be sufficient.

[Formula 3]

In formula (3), R ^{3 To} R ^{5 Are} each independently C ₁ ~ C ₆ Alkyl group; p is 2 and q is an integer of 0-3; k1 and k2 are each independently an integer of 0 to 4;

[Formula 4]

In formula (4), R ^{3 To} R ^{6 Are} each independently a C ₁ ~ C ₆ Alkyl group; p1 and p2 are each independently an integer of 0 to 2, p1 + p2 is 2, p1 + q1 is an integer of 3 or less, and p2 + q2 is an integer of 4 or less; k1 and k2 are the integers of 0-4 each independently.

In addition, the reaction for redistributing the polyphenylene ether in the presence of (a) 9,10-dihydro-9-oxa-10- (dihydroxyaryl) -10-phosphaphenanthrene 10-oxide is carried out using a radical initiator and And / or in the presence of a catalyst.

The radical initiator and catalyst may be used conventionally known in the art. Examples of radical initiators include t-butylperoxy isopropylmonocarbonate, t-butylperoxy 2-ethylhexyl carbonate, benzoyl peroxide and acetyl Acetyl peroxide, di-t-butyl peroxide, t-butyl peroxylaurate, t-butylperoxybenzoate, It is not limited to this. The radical initiator may be used in an amount of 0.1 to 5 parts by weight based on 10 to 60 parts by weight of the polyphenylene ether.

Further non-limiting examples of such catalysts include cobalt naphthanate. The catalyst may be used in an amount of 0.001 to 0.5 parts by weight based on 10 to 60 parts by weight of the polyphenylene ether.

The method for synthesizing the modified polyphenylene ether resin by redistributing the polyphenylene ether is not particularly limited and conventional methods known in the art may be applied. For example, polyphenylene ether, 9,10-dihydro-9-oxa-10- (dihydroxyaryl) -10-phosphaphenanthrene 10-oxide and a radical initiator are mixed in a solvent or in a solvent-free manner. By heating, a modified polyphenylene ether resin can be obtained. In this case, the solvent may be a hydrocarbon solvent such as benzene or toluene, but is not particularly limited thereto. In addition, the reaction temperature and the reaction time can be appropriately adjusted according to the number average molecular weight of the desired polyphenylene ether resin, non-limiting examples can be reacted for 10 minutes to 10 hours.

In addition, in the present invention, (b) the dicyclopentadiene epoxy resin of the general formula (1) is a multifunctional resin, and has a hydrophobic double-cyclic hydrocarbon group, so there is little electron polarization phenomenon, which may contribute to lowering the dielectric constant of the copper foil laminate. .

The dicyclopentadiene epoxy resin of the general formula (1) is preferably an epoxy equivalent of 200 to 500, the dicyclopentadiene epoxy resin of the general formula (1) having an epoxy equivalent outside the above range is insufficient strength of the substrate, heat resistance lowering There may be problems such as foaming of the surface of the prepreg and the like, which is not preferable. In the present invention, 'epoxy equivalent' is defined as the molecular weight of the epoxy resin per epoxy group.

In addition, the dicyclopentadiene epoxy resin of the general formula (1) in the present invention is preferably included in a ratio of 10 to 40 parts by weight with respect to 10 to 60 parts by weight of polyphenylene ether, the effect of lowering the dielectric constant outside the range It is not preferable because there may be a problem such as a lack of molding processability or no.

In the present invention, the epoxy curing agent (c) uses the alkylphenol aldehyde novolac epoxy curing agent of the formula (2), and significantly improved the dielectric properties and heat resistance of the cured product compared to the dicyandiamide curing agent or acid anhydride curing agent used in the prior art It is effective to let.

Examples of the alkylphenol aldehyde novolac epoxy curing agent of Chemical Formula 2 include an alkylphenol aldehyde novolac curing agent such as para-t-butylphenol acetaldehyde novolac, para-t-butylphenol formaldehyde novolac, para-t-butylphenol propion Aldehyde novolacs, para-methylphenol acetaldehyde novolacs, or para-t-octylphenol acetaldehyde novolacs, and the like. In addition, the epoxy curing agent may be used alone or in combination of two or more.

In the present invention, the alkylphenol aldehyde novolac epoxy curing agent of the formula (2) is preferably a hydroxyl equivalent weight of 100 ~ 1000, less than 100, the improvement of the dielectric properties is insignificant, the crosslinking density of the polymer to be cured when it exceeds 1000 As heat resistance may worsen, it is not preferable. In the present invention, the 'hydroxyl equivalent' refers to the molecular weight of the hydroxyl compound per hydroxyl group.

In addition, the alkylphenol aldehyde novolac epoxy curing agent of the formula (2) is preferably included in a ratio of 10 to 40 parts by weight with respect to 10 to 60 parts by weight of polyphenylene ether, the crosslinking density of the cured product is less than 10 parts by weight Deterioration in strength and heat resistance may occur, and when it exceeds 40 parts by weight, there may be a problem in that the molding becomes difficult because of poor fluidity.

The resin composition for a printed circuit board of the present invention may further include a curing accelerator (d). The curing accelerator is preferably used in consideration of the curing rate, and more preferably 2-ethyl-4-methyl imidazole or 2-methyl imidazole may be used.

In addition, the curing accelerator is preferably included in 0.01 to 1 parts by weight with respect to 10 to 60 parts by weight of polyphenylene ether, less than 0.01 parts by weight does not cure or requires high temperature conditions or long time to cure, while 1 When it exceeds a weight part, a problem may arise in the maintenance safety of a resin composition, or the characteristic of hardened | cured material may fall.

The resin composition for a printed circuit board of the present invention may further include additives such as inorganic fillers in addition to the above components. The inorganic filler may be silica, alumina, aluminum hydroxide, calcium carbonate, clay, talc, silicon nitride, boron nitride, titanium oxide, barium titanate, or titanate, but is not limited thereto.

The resin composition for a printed circuit board of the present invention may be prepared by uniformly mixing a modified polyphenylene ether resin, a dicyclopentadiene epoxy resin of Formula 1, an alkylphenol aldehyde novolac curing agent of Formula 2, and other additives. have.

On the other hand, the composite substrate of the present invention is formed by coating or impregnating the resin composition according to the invention on the substrate and then dried, preferably a composite substrate for a printed circuit board.

At this time, the drying may be made at 20 ~ 200 ℃ non-limiting examples.

The substrate may be at least one selected from the group consisting of glass fiber cloth, glass fiber nonwoven fabric, polyamide fiber cloth, polyamide fiber nonwoven fabric, polyester fiber cloth and polyester fiber nonwoven fabric, wherein the composite material may be a prepreg for a printed circuit board. desirable.

In addition, the substrate may be at least one selected from the group consisting of a glass plate, a polymer film, and a metal plate, but is not limited thereto. In addition, the polymer film and the metal plate are not particularly limited, and a film made of a conventional polymer known in the art, and a plate made of a conventional metal or alloy known in the art may be used. At this time, when the metal plate is a copper foil, the composite substrate formed by coating the resin composition according to the present invention on copper foil and drying can be used as a copper foil laminated plate.

The coating method may use a conventional coating method known in the art, and includes, but is not limited to, lip coating, die coating, roll coating, comma coating, or these Various methods, such as a mixing method, can be used.

In addition, the composite substrate of the present invention may be a laminate of two or more composite substrates formed by coating or impregnating a resin composition according to the present invention on a substrate and then drying them.

In the present invention, the copper foil laminate is formed by laminating the composite substrate and the copper foil according to the present invention and heating and pressing. In this case, the composite base material is preferably a prepreg. In addition, heating pressurization conditions at the time of lamination shaping | molding can be suitably set according to the thickness of the laminated board to manufacture, the kind of resin composition concerning this invention, etc.

Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the following examples are merely to illustrate the present invention and the present invention is not limited by the following examples.

(Example 1)

(Production of Resin Composition)

As shown in Table 1, 30 parts by weight of polyphenylene ether (Nornyl PX9701, GE) having a number average molecular weight of 2000 to 20000, 9,10-dihydro-9-oxa-10- (2,5-dihydroxy 2 parts by weight of phenyl) -10-phosphaphenanthrene 10-oxide (HCA-HQ, Sanko), 0.9 parts by weight of t-butylperoxy isopropyl monocarbonate (PB-I, Nippon Oil & Fats) as a radical initiator And 0.016 parts by weight of cobalt naphtanate having a cobalt content of 6% as a catalyst, and reacted at 90 ° C. for 60 minutes to prepare a polyphenylene ether resin modified to a number average molecular weight of 5800.

35 parts by weight of dicyclopentadiene epoxy resin (HP-7200, Epiclon) to the modified polyphenylene ether resin, 35 parts by weight of para-t-butylphenol acetaldehyde novolac as an alkylphenol novolac curing agent and a curing accelerator 0.3 weight part of 2-ethyl-4-methylimidazole was added, and it stirred about 1 hour, and prepared the resin composition.

(Manufacture of Copper Foil Laminate)

The prepared resin composition was impregnated into glass fiber (7628 or 2116, manufactured by Baotek Co., Ltd.), and dried for 5 to 10 minutes in a 150 ° C dryer to prepare a prepreg having a resin content of 43 to 52%.

8 sheets of prepregs were laminated, and copper foils having a thickness of 35 μm were laminated on the upper and lower sides, and then molded at 120 ° C. under a pressure of 40 kgf / cm ² at a temperature of 180 ° C. to prepare a double-sided copper foil laminate having a thickness of 1.0 to 1.6 mm. It was.

(Example 2)

As shown in Table 1 in Example 1 25 parts by weight of dicyclopentadiene epoxy resin (HP-7200, Epiclon, Inc.), 45 parts by weight of para-t-butylphenol acetaldehyde novolak as an alkylphenol novolak curing agent Except that, it was carried out in the same manner as in Example 1 to prepare a resin composition and a copper foil laminate.

(Example 3)

Example 1, except that benzoyl peroxide was used instead of t-butylperoxy isopropyl monocarbonate (PB-I, Nippon Oil & Fats) as a radical initiator in Example 1, as shown in Table 1 below. The resin composition and the copper foil laminated board were manufactured by the same method as the above.

(Example 4)

In Example 1, benzoyl peroxide is used instead of t-butylperoxy isopropyl monocarbonate (PB-I, Nippon Oil & Fats) as a radical initiator, and dicyclopentadiene epoxy resin ( HP-7200, Epiclon Co.) 25 parts by weight, except that 45 parts by weight of para-t- butylphenol acetaldehyde novolac as the alkylphenol novolak curing agent was carried out in the same manner as in Example 1, the resin composition and copper foil Laminates were prepared.

(Comparative Example 1)

0.3 weight of bisphenol A in place of 9,10-dihydro-9-oxa-10- (2,5-dihydroxyphenyl) -10-phosphaphenanthrene 10-oxide as shown in Table 1 below Part, except that 0.27 parts by weight of t-butylperoxy isopropyl monocarbonate (PB-I, Nippon Oil & Fats) as a radical initiator and 0.008 parts by weight of cobalt naphtanate having a cobalt content of 6% as a catalyst were used. It carried out by the same method as Example 1, and manufactured the resin composition and the copper foil laminated board.

(Comparative Example 2)

0.3 weight of bisphenol A in place of 9,10-dihydro-9-oxa-10- (2,5-dihydroxyphenyl) -10-phosphaphenanthrene 10-oxide as shown in Table 1 above Parts, except that 0.27 parts by weight of benzoyl peroxide instead of t-butylperoxy isopropyl monocarbonate (PB-I, Nippon Oil & Fats) as a radical initiator and 0.008 parts by weight of cobalt naphtanate having a cobalt content of 6% as a catalyst were used. Was carried out in the same manner as in Example 4 to prepare a resin composition and a copper foil laminate.

(Comparative Example 3)

As shown in Table 1, 36 parts by weight of brominated epoxy resin (YDB-400, Kukdo Chemical Co., Ltd.) having a bromine content of 20 to 50%, 30 parts by weight of dicyclopentadiene epoxy resin (HP-7200, Epiclon), alkyl 34 parts by weight of para-t-butylphenol acetaldehyde novolak as a phenol novolak curing agent and 0.5 parts by weight of 2-ethyl-4-methylimidazole as a curing accelerator were mixed and stirred for about 1 hour to prepare a resin composition. Then, it carried out by the same method as Example 1, and manufactured the copper foil laminated board.

division Example Comparative example One 2 3 4 One 2 3 Polyphenylene Ether (PPE) 30 30 30 30 30 30 - Bisphenol A - - - - 0.3 0.3 - 9,10-dihydro-9-oxa-10- (2,5-dihydroxyphenyl) -10-phosphaphenanthrene 10-oxide (HCA-HQ) 2 2 2 2 - - - PB-I (radical initiator) 0.9 0.9 - - 0.27 - - Benzoyl peroxide (radical initiator) - - 0.9 0.9 - 0.27 - Cobalt Naphtanate (catalyst) 0.016 0.016 0.016 0.016 0.008 0.008 - Modified Polyphenylene Ether Molecular Weight 5800 5800 3100 3100 11000 2800 - Brominated epoxy resin - - - - - - 36 Dicyclopentadiene Epoxy Resin 35 25 35 25 35 25 30 Alkylphenol Novolac Curing Agent 35 45 35 45 35 45 34 2-ethyl-4-methylimidazole (curing accelerator) 0.3 0.3 0.3 0.3 0.3 0.3 0.5

Experimental Example

The physical properties of the copper foil laminates prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were measured by the following methods, and the results are shown in Table 2 below.

(1) Glass transition temperature (T _g ): The copper foil layer of the copper foil laminated sheet was removed by etching, and then measured by using a DSC (Differential Scanning Calorimeter).

(2) permittivity: IPC TM-650. It was measured using a material analyzer according to the test standard of 2.5.5.1.

(3) Lead heat resistance: The time at which abnormality began to occur was measured after putting a sample cut into a size of 5 cm x 5 cm in a lead bath at 288 ° C.

(4) Copper foil adhesive strength: IPC-TM-650. It measured according to the test specification of 2.4.8.

(5) Flame retardant: Measured according to UL 94 standard.

division Example Comparative example One 2 3 4 One 2 3 Glass transition temperature (Tg, ℃) 196 202 191 201 176 186 178 Dielectric constant (R / C = 52% at 1MHz) 3.5 3.4 3.5 3.4 3.7 3.7 4.1 Lead heat resistance (@ 288) 600 seconds 600 seconds 600 seconds 600 seconds 120 seconds 180 seconds 390 seconds Copper Bond Strength (kN / m) 1.4 1.2 1.5 1.3 1.1 0.9 1.5 Flame retardant V-0 V-0 V-0 V-0 V-1 V-1 V-0

As shown in Table 2, polyphenylene ether was redistributed under 9,10-dihydro-9-oxa-10- (2,5-dihydroxyphenyl) -10-phosphaphenanthrene 10-oxide. Examples 1 to 4 using modified polyphenylene ether resins were prepared by redistributing and reacting polyphenylene ether under conventional bisphenol A to use Comparative Examples 1 to 2 and polyphenylene ether. It was confirmed that the properties such as glass transition temperature, dielectric constant, heat resistance, adhesive strength and flame retardancy were improved compared to the case of Comparative Example 3 without using the resin.

According to the present invention, polyphenylene ether is redistributed using 9,10-dihydro-9-oxa-10- (dihydroxyaryl) -10-phosphaphenanthrene 10-oxide instead of conventionally used bisphenol A. Can react. In addition, the use of a resin composition comprising a polyphenylene ether resin modified by such a redistribution reaction has a relatively high glass transition temperature, excellent heat resistance, adhesive strength and flame retardancy, and is suitable for high speed and high frequency of signals. The copper foil laminated board which has dielectric constant can be manufactured.

Claims (13)

(a) polyphenylene ether resin modified by redistribution of polyphenylene ether in the presence of 9,10-dihydro-9-oxa-10- (dihydroxyaryl) -10-phosphaphenanthrene 10-oxide ; (b) a dicyclopentadiene epoxy resin of formula (1); And (c) Resin composition for a printed circuit board comprising an alkylphenol aldehyde novolac curing agent of the formula (2). [Formula 1]

In formula 1, m is an integer of 0 or more; [Formula 2]

In formula (2), R ¹ is a C ₁ to C ₁₂ alkyl group, C ₁ to C ₆ alkyl group, C ₅ to C ₇ cycloalkyl group, or C ₆ to C ₂₄ aromatic hydrocarbon group; R ² is hydrogen or an alkyl group of C ₁ to C ₁₂ ; n is an integer of 0 or more. According to claim 1, The polyphenylene ether is 10 to 60 parts by weight; The 9,10-dihydro-9-oxa-10- (dihydroxyaryl) -10-phosphaphenanthrene 10-oxide is 0.1 to 5 parts by weight; The dicyclopentadiene epoxy resin is 10 to 40 parts by weight; And the alkylphenol aldehyde novolac curing agent is 10 to 40 parts by weight. The group of claim 1, wherein the 9,10-dihydro-9-oxa-10- (dihydroxyaryl) -10-phosphaphenanthrene 10-oxide is a group consisting of a compound of Formula 3 and a compound of Formula 4 Resin composition for a printed circuit board, characterized in that at least one compound selected from. [Formula 3]

In formula (3), R ^{3 To} R ^{5 Are} each independently C ₁ ~ C ₆ Alkyl group; p is 2 and q is an integer of 0-3; k1 and k2 are each independently an integer of 0 to 4; [Formula 4]

In formula (4), R ^{3 To} R ^{6 Are} each independently a C ₁ ~ C ₆ Alkyl group; p1 and p2 are each independently an integer of 0 to 2, p1 + p2 is 2, p1 + q1 is an integer of 3 or less, and p2 + q2 is an integer of 4 or less; k1 and k2 are the integers of 0-4 each independently. The resin composition of claim 1, wherein the redistribution reaction (a) is carried out in the presence of a radical initiator or a catalyst or a radical initiator and a catalyst. The resin composition for a printed circuit board of claim 1, wherein the (b) dicyclopentadiene epoxy resin has an epoxy equivalent of 200 to 500. The resin composition for a printed circuit board of claim 1, wherein the (c) alkylphenol aldehyde novolac curing agent has a hydroxyl equivalent of 100 to 1000. The method of claim 1, wherein the (c) alkylphenol aldehyde novolac curing agent is para-t-butyl phenol acetaldehyde novolac, para-t-butylphenol formaldehyde novolac, para-t-butylphenol propionaldehyde novolac, A resin composition for a printed circuit board, characterized in that at least one member selected from the group consisting of para-methylphenol acetaldehyde novolac and para-t-octylphenol acetaldehyde novolac. The resin composition for a printed circuit board according to claim 1, further comprising (d) a curing accelerator. The resin composition of claim 8, wherein the curing accelerator (d) is an imidazole series curing accelerator. A composite substrate formed by coating or impregnating a resin composition according to any one of claims 1 to 9 on a substrate, followed by drying. The method of claim 10, wherein the substrate is at least one member selected from the group consisting of glass fiber cloth, glass fiber nonwoven fabric, polyamide fiber cloth, polyamide fiber nonwoven fabric, polyester fiber cloth and polyester fiber nonwoven fabric, The composite substrate is a composite substrate, characterized in that the prepreg for a printed circuit board. The composite substrate of claim 10, wherein the substrate is at least one selected from the group consisting of a glass plate, a polymer film, and a metal plate. A copper foil laminated sheet formed by laminating the composite base material and the copper foil of claim 10 and heating and pressing.