JP2009191218A - Circuit board resin composition, prepreg and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a circuit board resin composition which has a low dielectric constant and dissipation factor and excels in heat resistance and adhesion, a prepreg and a laminate which use the same. <P>SOLUTION: The circuit board resin composition comprises a compound containing two or more maleimide groups in the molecule such as 2,2'-[4-(4-maleimidophenoxy)phenyl]propane and bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane and a compound containing one or more styryl groups in the molecule such as 1-phenyl-3-(4-t-butylstyryl)-5-(4-t-butylphenyl)pyrazoline, and the prepreg and the laminate use the same. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a circuit board resin composition, a prepreg, and a laminate.

  Information processing devices such as notebook personal computers and mobile phones are required to be faster, and the CPU clock frequency is higher. Therefore, a high signal propagation speed is required, and a printed board having a low dielectric constant and dielectric loss tangent is required for the high speed.

In order to reduce the dielectric constant and dielectric loss tangent, it is common practice to incorporate a compound containing two or more maleimide groups in the molecule into the molecular structure of the thermosetting resin. Examples of a method for incorporating a compound containing two or more maleimide groups in the molecule into a thermosetting resin include a method of copolymerizing with a cyanate resin and a method of copolymerizing with an epoxy resin. However, when copolymerized with a cyanate resin, the dielectric constant and dielectric loss tangent are excellent, but since the water absorption is large, the dielectric properties after moisture absorption are inferior, and the solder heat resistance is not sufficient.
In addition, when copolymerized with an epoxy resin, a polar group is generated after curing, so that there is a disadvantage that the dielectric constant and dielectric loss tangent are increased.
JP-A-6-306166 JP-A-8-225668

  The present invention provides a resin composition for a circuit board having a low dielectric constant and dielectric loss tangent and having excellent heat resistance and adhesion, and a prepreg and a laminate using the same.

Such an object is achieved by the present invention described in the following (1) to (9).
(1) For a circuit board comprising a compound (A) containing two or more maleimide groups in the molecule and a compound (B) containing one or more styryl groups in the molecule Resin composition.
(2) The compound (B) is a resin composition for circuit boards according to the above (1) represented by the following general formula (1).

(3) The resin composition for a circuit board according to (1), wherein the compound (B) is represented by the following general formula (2).

(4) The resin composition for a circuit board according to any one of (1) to (3), wherein the compound (A) is 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane.
(5) The circuit board resin composition according to any one of (1) to (4), wherein the compound (A) is bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane.
(6) The resin for a circuit board according to any one of the above (1) to (5), wherein the cured product of the resin composition for a circuit board has a dielectric constant at 1 GHz of 2.3 or more and 3.3 or less. Composition.
(7) The resin for circuit boards according to any one of the above (1) to (6), wherein the cured product of the resin composition for circuit boards has a dielectric loss tangent at 1 GHz of 0.005 or more and 0.018 or less. Composition.
(8) A prepreg obtained by impregnating a base material with the resin composition for a circuit board according to any one of (1) to (7).
(9) A laminate comprising one or more of the prepregs described in (8) above.

  It is possible to provide a resin composition for a circuit board having a low dielectric constant and dielectric loss tangent and having excellent heat resistance and adhesion, and a prepreg and a laminate using the same.

  Hereinafter, the resin composition for circuit boards, the prepreg, and the laminate of the present invention will be described.

  The resin composition for circuit boards of the present invention forms a resin composition directly on a metal foil as a substrate and is used as a copper foil with a resin, or a glass fiber substrate as a substrate is impregnated with a resin composition as a prepreg, It can be used as an interlayer insulating material for a multilayer substrate, or can be used as a laminate by laminating prepreg and metal foil and heating and pressing.

  The resin composition for circuit boards of the present invention contains a compound containing two or more maleimide groups in the molecule and a compound containing one or more styryl groups in the molecule (excluding styrene). It is what.

  Moreover, the prepreg of the present invention is characterized in that a base material is impregnated with the above-mentioned resin composition for circuit boards.

  Moreover, the laminated board of the present invention is formed by molding one or more of the above-described prepregs.

  First, the circuit board resin composition of the present invention will be described.

  The resin composition for circuit boards of this invention contains the compound (A) containing two or more maleimide groups in a molecule | numerator. Thereby, the dielectric constant and dielectric loss tangent of a laminated board can be improved, and it has heat resistance.

  The compound (A) is not particularly limited, but 4,4′-diphenylmethane bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, 2,2 ′-[4- (4-maleimidophenoxy) phenyl] Propane, bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane, 4-methyl-1,3-phenylenebismaleimide, N, N′-ethylenedimaleimide, N, N′-hexamethylenedimaleimide And bismaleimide such as polyphenylmethanemaleimide. Considering a low water absorption rate, 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane and bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane are particularly preferable.

  The compound (A) may be used alone or in combination of two or more.

  The resin composition for circuit boards of the present invention contains a compound (B) containing one or more styryl groups in the molecule. Thereby, a dielectric constant and a dielectric loss tangent can be reduced, maintaining a low water absorption.

  The compound (B) is preferably a compound represented by the following general formula (1).

  Further, as the compound (B), a pyrazoline compound represented by the following general formula (2) has a large molecular volume and is preferable for reducing the dielectric constant and dielectric loss tangent.

  Although it does not specifically limit as said compound (B), Anethole, isosafrole, stilbene, 2-methylstilbene, 4-methylstilbene, 3,4 ', 5-trimethoxystilbene, 3,5-dimethoxystilbene, 4, 4′-dimethoxystilbene, 4,4′-dimethylstilbene, 1-acetoxy-2-methoxy-4- (1-propenyl) benzene, 1-benzyloxy-2-methoxy-4- (1-propenyl) benzene, 4 -(1-propenyl) -1,2-dimethoxystilbene, 1-phenyl-3-styryl-5-phenylpyrazoline, 1-phenyl-3- (4-tbutylstyryl) -5- (4-tbutylphenyl) ) A compound containing one styryl group in a molecule such as pyrazoline, 4,4′-bis (2-methylstyryl) biphe Le, such as 4,4'-bis (2-methoxy-styryl) compounds containing two styryl group in the molecule such as biphenyl and the like.

  By using the compound (B), the dielectric constant and dielectric loss tangent can be reduced while maintaining a low water absorption.

  The double bond of the maleimide group of the compound (A) is a double bond in an electron-deficient state due to two carbonyl groups. On the other hand, the double bond of the styryl group of the compound (B) is a double bond in an electron excess state due to the flow of electrons from the phenyl moiety. For this reason, the double bond of a maleimide group and the double bond of a styryl group react easily by heating.

  By using the compound (A), the reaction point becomes two or more, a network structure is taken, and the heat resistance is improved.

  Moreover, since a polar group such as a hydroxyl group is not generated by the reaction of the double bond of the maleimide group and the double bond of the styryl group, the dielectric constant and the dielectric loss tangent can be reduced while maintaining a low water absorption. The resin composition for a circuit board according to the present invention can have a low water absorption as well as its low dielectric constant and low dielectric loss tangent even when a compound containing two or more maleimide groups in the molecule is used. It is.

  In particular, 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane or bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane is used as compound (A) and compound (B) is used. When 1-phenyl-3- (4-tbutylstyryl) -5- (4-tbutylphenyl) pyrazoline is used, the volume occupied by the molecule increases, resulting in low water absorption as well as low dielectric constant and low dielectric loss tangent. preferable.

  The equivalent ratio of the compound (A) and the compound (B) is preferably 0.8 to 1.2. When the equivalent ratio is less than 0.8 or exceeds 1.2, an unreacted compound remains and heat resistance is lowered, which is not preferable.

  The cured product of the resin composition for circuit boards of the present invention has a dielectric constant at 1 GHz of 2.3 or more and 3.3 or less, and a dielectric loss tangent at 1 GHz of 0.005 or more and 0.018 or less. Preferably there is.

  The cured product of the circuit board resin composition means a state in which the reaction of the functional group of the curable resin component in the curable resin composition constituting the circuit board resin composition is substantially completed, For example, it can be evaluated by measuring the calorific value with a differential scanning calorimetry (DSC) device, and specifically indicates a state in which this calorific value is hardly detected.

  As a condition for obtaining such a cured product of the resin material, for example, it is preferable to treat at 120 to 220 ° C. for 30 to 180 minutes, and it is particularly preferable to treat at 150 to 200 ° C. for 45 to 120 minutes.

  In addition, for example, maleimide groups and styrene compounds are known to polymerize, but compounds having an α monosubstituted double bond such as styrene, or α and α ′ such as α-methylstyrene are substituted. The double bond of a compound having a heavy bond is not preferable because it has high reactivity with the maleimide compound and it is difficult to control the reaction. In contrast, a compound having a styryl group has α and β disubstituted double bonds, but this double bond is sterically hindered, so the reactivity with the maleimide compound is not so high, and the reaction can be controlled. Suitable for prepreg production. However, styrene may be included as other resins described later.

  The resin composition for circuit boards of the present invention contains the above-mentioned compound (A) and compound (B) as essential components, but other resins such as an epoxy resin and a phenoxy resin are within the scope of the present invention. , Polyimide resins, phenol resins, etc., and addition of curing agents, curing accelerators, flame retardants, coupling agents, fillers, and other components such as monomaleimides such as N-phenylmaleimide and N-cyclohexylmaleimide. Absent.

  Next, the prepreg will be described.

  The prepreg of the present invention is obtained by impregnating a base material with the above-described resin composition for circuit boards. Thereby, the prepreg excellent in various characteristics, such as heat resistance, can be obtained.

  Examples of the base material used in the prepreg of the present invention include glass fiber base materials such as glass fiber cloth and glass non-woven cloth, inorganic fiber base materials such as fiber cloth and non-fiber cloth containing inorganic compounds other than glass, and aromatic polyamide resins. And organic fiber base materials composed of organic fibers such as polyamide resin, aromatic polyester resin, polyester resin, polyimide resin, and fluororesin. Among these base materials, glass fiber base materials represented by glass woven fabric are preferable in terms of strength and water absorption.

  The method for impregnating the substrate with the circuit board resin composition obtained in the present invention is, for example, a method in which the resin composition for circuit board is dissolved in a solvent to prepare a resin varnish, and the substrate is immersed in the resin varnish. And a method of applying a resin varnish to a substrate with various coater devices, a method of spraying a resin varnish onto a substrate with a spray device, and the like. Among these, the method of immersing the base material in the resin varnish is preferable. Thereby, the impregnation property of the resin composition for circuit boards with respect to a base material can be improved. In addition, when a base material is immersed in a resin varnish, a normal impregnation coating device can be used.

  The solvent used in the resin varnish desirably has good solubility in the resin composition for circuit boards, but a poor solvent may be used as long as it does not have an adverse effect. Examples of the solvent exhibiting good solubility include dimethylformamide.

Although the solid content in the resin varnish is not particularly limited, the solid content of the resin composition for circuit boards is preferably 40 to 80% by weight, and particularly preferably 50 to 65% by weight. Thereby, the impregnation property to the base material of a resin varnish can further be improved.
A prepreg can be obtained by impregnating the base material with the resin composition for a circuit board and drying at a predetermined temperature, for example, 80 to 200 ° C.

  Next, a laminated board is demonstrated.

  The laminate of the present invention is formed by molding at least one prepreg described above. Thereby, the laminated board which has the outstanding heat resistance and adhesiveness, and whose dielectric constant and dielectric loss tangent are low can be obtained.

  In the case of a single prepreg, a metal foil or film is stacked on both upper and lower surfaces or one surface.

  Two or more prepregs can be laminated. When two or more prepregs are laminated, a metal foil or film is laminated on the outermost upper and lower surfaces or one surface of the laminated prepreg.

  Next, a laminate can be obtained by heating and pressurizing a laminate of a prepreg and a metal foil or the like.

  The heating temperature is not particularly limited, but is preferably 150 to 240 ° C, and particularly preferably 180 to 220 ° C.

  Moreover, the pressure to pressurize is not particularly limited, but is preferably 2 to 5 MPa, and particularly preferably 2.5 to 4 MPa.

Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to this.
Example 1
(1) Preparation of resin varnish 38 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane, 1-phenyl-3- (4-tbutylstyryl) -5- (4-tbutyl) N-methyl-2-pyrrolidone was added to 62 parts by weight of phenyl) pyrazoline, and the mixture was heated at 100 ° C. and adjusted so as to have a nonvolatile content of 50% to obtain a resin varnish.
(2) Manufacture of prepreg Using the above-mentioned resin varnish, 100 parts by weight of glass fiber cloth (thickness 0.18 mm, manufactured by Nitto Boseki Co., Ltd.) was impregnated with 80 parts by weight of resin varnish in a solid content, and 190 ° C. The prepreg having a resin content of 44.4% by weight was produced by drying in a drying oven for 5 minutes.
(3) Manufacture of laminated board Six sheets of the above prepregs are stacked, electrolytic copper foils with a thickness of 35 μm are stacked on top and bottom, and heat-press molding is performed at a pressure of 4 MPa and a temperature of 220 ° C. for 180 minutes, and both sides have a thickness of 1.2 mm. A copper clad laminate was obtained.
(Example 2)
20 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane and 80 parts by weight of 1-phenyl-3- (4-tbutylstyryl) -5- (4-tbutylphenyl) pyrazoline Except that, a resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg and a laminate.
(Example 3)
50 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane and 50 parts by weight of 1-phenyl-3- (4-tbutylstyryl) -5- (4-tbutylphenyl) pyrazoline Except that, a resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg and a laminate.
Example 4
34 parts by weight of bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane, 66 parts by weight of 1-phenyl-3- (4-tbutylstyryl) -5- (4-tbutylphenyl) pyrazoline Except that, a resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg and a laminate.
(Example 5)
A resin varnish was prepared in the same manner as in Example 1 except that 60 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane and 40 parts by weight of t-stilbene were prepared. I got a plate.
(Example 6)
Example 1 with the exception that 56 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane and 44 parts by weight of 1-acetoxy-2-methoxy-4- (1-propenyl) benzene were used. A resin varnish was prepared in the same manner as above to obtain a prepreg and a laminate.
(Example 7)
34 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane and 56 parts by weight of 1-phenyl-3- (4-tbutylstyryl) -5- (4-tbutylphenyl) pyrazoline A resin varnish was prepared in the same manner as in Example 1 except that 10 parts by weight of bisphenol A type phenoxy resin (1256 manufactured by Japan Epoxy Resin Co., Ltd.) was obtained, and a prepreg and a laminate were obtained.
(Example 8)
36 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane and 59 parts by weight of 1-phenyl-3- (4-tbutylstyryl) -5- (4-tbutylphenyl) pyrazoline A resin varnish was prepared in the same manner as in Example 1 except that 5 parts by weight of triphenylphosphine oxide was used to obtain a prepreg and a laminate.
Example 9
34 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane and 61 parts by weight of 1-phenyl-3- (4-tbutylstyryl) -5- (4-tbutylphenyl) pyrazoline A resin varnish was prepared in the same manner as in Example 1 except that 5 parts by weight of styrene was used to obtain a prepreg and a laminate.
(Comparative Example 1)
Instead of using 20 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane and a compound containing one or more styryl groups in the molecule, cyanate resin (B-40S manufactured by Ciba Geigy) ) Was used in the same manner as in Example 1 except that 80 parts by weight were used to obtain a prepreg and a laminate.
(Comparative Example 2)
50 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane, without using a compound containing one or more styryl groups in the molecule, instead of cresol novolak epoxy resin (Dainippon Ink Chemical Co., Ltd.) A resin varnish was prepared in the same manner as in Example 1 except that 15 parts by weight of N-690 manufactured by Kogyo Co., Ltd. and 35 parts by weight of phenol novolac resin (PR-51470 manufactured by Sumitomo Bakelite Co., Ltd.) were used. Got.
The following evaluation was performed about the laminated board obtained by each Example and the comparative example. Each evaluation is shown below together with the evaluation method. The obtained results are shown in Table 1.

1. Evaluation methods
(1) Measurement of dielectric characteristics of resin at 1 GHz The measurement of dielectric characteristics of resin at 1 GHz is performed by applying a resin composition for a circuit board to a carrier film, heating, pressing and removing the carrier film. It was measured by the plate resonator method.
(2) Measurement of dielectric characteristics of laminated plate at 1 GHz The dielectric characteristics of the laminated plate at 1 GHz were measured by a triplate resonator method.
(3) Dielectric property measurement at 1 GHz after moisture absorption of the laminate plate The dielectric property measurement at 1 GHz after moisture absorption of the laminate plate was measured by immersing the laminate in water at 23 ° C. for 24 hours and then by the triplate resonator method. did.
(4) Solder heat resistance The solder heat resistance was measured in accordance with JIS C 6481. In the measurement, after performing a moisture absorption treatment for 2 hours after boiling, it was immersed in a solder bath at 288 ° C. for 120 seconds and then examined for abnormal appearance.
(5) Peel strength The peel strength was measured in accordance with JIS C 6481.

As is clear from the table, Examples 1 to 9 show the circuit board resin composition of the present invention containing a compound containing two or more maleimide groups in the molecule and one or more styryl groups in the molecule. The laminate used was excellent in heat resistance and adhesion, and had a sufficiently low dielectric constant and dielectric loss tangent.
In contrast, in Comparative Example 1, a cyanate resin was used in place of the compound containing one or more styryl groups in the molecule, but the dielectric properties after moisture absorption deteriorated and the solder heat resistance after moisture absorption also deteriorated. Dielectric constant and dielectric loss tangent did not become low enough. In Comparative Example 2, since an epoxy resin and a phenol novolac resin were used in place of the compound containing one or more styryl groups in the molecule, the dielectric constant and dielectric loss tangent were not sufficiently lowered.

  The resin composition for circuit boards, the prepreg, and the laminate of the present invention can be adapted to miniaturization and weight reduction, and is suitable for a printed wiring board required for high heat resistance, adhesion, and high signal propagation speed.

Claims (9)

A compound (A) containing two or more maleimide groups in the molecule;
A compound (B) containing one or more styryl groups in the molecule;
A resin composition for circuit boards, comprising: The said compound (B) is a resin composition for circuit boards of Claim 1 represented by following General formula (1).

The said compound (B) is a resin composition for circuit boards of Claim 1 represented by following General formula (2).

  4. The circuit board resin composition according to claim 1, wherein the compound (A) is 2,2 '-[4- (4-maleimidophenoxy) phenyl] propane.   5. The circuit board resin composition according to claim 1, wherein the compound (A) is bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane.   The resin composition for a circuit board according to any one of claims 1 to 5, wherein a cured product of the resin composition for a circuit board has a dielectric constant at 1 GHz of 2.3 or more and 3.3 or less.   The circuit board resin composition according to any one of claims 1 to 6, wherein the cured product of the circuit board resin composition has a dielectric loss tangent at 1 GHz of 0.005 or more and 0.018 or less.   A prepreg obtained by impregnating a base material with the circuit board resin composition according to any one of claims 1 to 7.   A laminate obtained by molding one or more prepregs according to claim 8.