JP5136331B2 - Circuit board resin composition, circuit board prepreg and laminate - Google Patents

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 may not be sufficient.

In addition, when copolymerized with an epoxy resin, a polar group is generated after curing, so that the dielectric constant and dielectric loss tangent may increase.
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 ( 7 ).
(1) Compound (A) containing two or more maleimide groups in the molecule and compound containing one styryl group and one phenolic hydroxyl group in the molecule represented by the following general formula (1) (B And an epoxy resin (C) containing one or more epoxy groups in the molecule .

( 2 ) The circuit board resin composition according to (1 ), wherein the compound (A) is 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane.
( 3 ) The resin composition for circuit boards according to (1 ), wherein the compound (A) is bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane.
( 4 ) The circuit board according to any one of (1) to ( 3 ), wherein the cured product of the resin composition for circuit boards has a dielectric constant at 1 GHz of 2.3 or more and 3.5 or less. Resin composition.
( 5 ) The circuit board according to any one of (1) to ( 4 ), wherein the cured product of the resin composition for a circuit board has a dielectric loss tangent at 1 GHz of 0.005 or more and 0.018 or less. Resin composition.
( 6 ) A prepreg for a circuit board , comprising a base material impregnated with the resin composition for a circuit board according to any one of (1) to ( 5 ).
( 7 ) A laminate comprising one or more circuit board prepregs as described in (6 ) above.

  ADVANTAGE OF THE INVENTION According to this invention, the dielectric constant and dielectric loss tangent are low, The resin composition for circuit boards which has the outstanding heat resistance and adhesiveness, and a prepreg and laminated board using the same can be provided.

  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 a circuit board of the present invention comprises a compound containing two or more maleimide groups in the molecule, a compound containing one or more styryl groups and one or more phenolic hydroxyl groups in the molecule, An epoxy resin containing one or more epoxy groups is contained therein.

  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 and one or more phenolic hydroxyl groups in the molecule. As a result, the dielectric constant and dielectric loss tangent can be reduced while maintaining a low water absorption, and high adhesion is exhibited.

  Although it does not specifically limit as said compound (B), Isoeugenol, 4- (1-propenyl) phenol, banitrop, 2-methyl-5- (1-propenyl) phenol, 2-ethyl-5- (1-propenyl) ) Phenol, resveratrol, 3,5-dihydroxystilbene, 3,3′-dihydroxystilbene and the like.

  Among these, as the compound (B), a compound represented by the following general formula (1) is preferable.

  The resin composition for circuit boards of the present invention includes an epoxy resin (C) containing one or more epoxy groups in the molecule. Thereby, high adhesiveness is expressed.

  The epoxy resin (C) is not particularly limited, but is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy. Examples thereof include resins, phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, and hydrogenated bisphenol A type epoxy resins.

  By using the compound (A) and the compound (B) in combination, the dielectric constant and dielectric loss tangent can be reduced while maintaining a low water absorption, and heat resistance can be obtained.

  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 the polar 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 hydroxyl group of the compound (B) easily reacts with the epoxy group of the compound (C). Thereby, the excellent characteristics of the epoxy resin can be incorporated into the resin skeleton, and in particular, the adhesion is improved by the reaction between the epoxy group and the hydroxyl group.

  The resin composition for circuit boards of the present invention has excellent solder heat resistance and adhesion 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 can have.

  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 equivalent ratio of the compound (B) and the compound (C) 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 3.5 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.

  The resin composition for a circuit board of the present invention contains the above-mentioned compound (A), compound (B) and compound (C) as essential components, but other resins, as long as the object of the present invention is not violated, For example, epoxy resins, phenoxy resins, polyimide resins, phenol resins, etc., and curing agents, curing accelerators, flame retardants, coupling agents, fillers, and other components such as monomaleimides such as N-phenylmaleimide and N-cyclohexylmaleimide , Stilbene, 1-acetoxy-2-methoxy-4- (1-propenyl) benzene, 4- (1-propenyl) -1,2-dimethoxybenzene and the like having a compound having one styryl group in the molecule Is fine.

  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 41.2 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane, 25.1 parts by weight of isoeugenol, cresol novolac epoxy resin (Dainippon Ink and Chemicals, Inc.) N-690, epoxy equivalent 210) 33.7 parts by weight of N-methyl-2-pyrrolidone was added to adjust the non-volatile content to 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)
3,9.2 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane, 28.7 parts by weight of isoeugenol, cresol novolac epoxy resin (N-690 manufactured by Dainippon Ink and Chemicals, epoxy equivalent) 210) A resin varnish was prepared in the same manner as in Example 1 except that the content was 32.1 parts by weight to obtain a prepreg and a laminate.
(Example 3)
43.4 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane, 21.2 parts by weight of isoeugenol, cresol novolac epoxy resin (N-690 manufactured by Dainippon Ink and Chemicals, epoxy equivalent) 210) A resin varnish was prepared in the same manner as in Example 1 except for 35.4 parts by weight, and a prepreg and a laminate were obtained.
Example 4
2,2 ′-[4- (4-Maleimidophenoxy) phenyl] propane 38.0 parts by weight, isoeugenol 23.2 parts by weight, phenol aralkyl type epoxy resin (Nippon Kayaku NC-3000H, epoxy equivalent 275) ) A resin varnish was prepared in the same manner as in Example 1 except that the content was 38.8 parts by weight, and a prepreg and a laminate were obtained.
(Example 5)
4,2 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane, 26.7 parts by weight of banitrop, cresol novolac epoxy resin (N-690 manufactured by Dainippon Ink and Chemicals, epoxy equivalent 210 ) A resin varnish was prepared in the same manner as in Example 1 except that the amount was 33.0 parts by weight, and a prepreg and a laminate were obtained.
(Example 6)
36.5 parts by weight of bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane, 27.1 parts by weight of isoeugenol, cresol novolac epoxy resin (N-690 manufactured by Dainippon Ink and Chemicals, epoxy equivalent) 210) A resin varnish was prepared in the same manner as in Example 1 except that 36.4 parts by weight were used, and a prepreg and a laminate were obtained.
(Comparative Example 1)
20 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane, a compound containing one or more styryl groups in the molecule and one or more phenolic hydroxyl groups in the molecule, and in the molecule A resin varnish was prepared in the same manner as in Example 1 except that 80 parts by weight of a cyanate resin (B-40S manufactured by Ciba Geigy Co., Ltd.) was used instead of an epoxy resin containing one or more epoxy groups. And the laminated board was obtained.
(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.
(Comparative Example 3)
62.1 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane and 37.9 parts by weight of isoeugenol are used, and an epoxy resin having one or more epoxy groups in the molecule is not used. Except that, a resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg and a laminate.
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 method
(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) 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.
(4) Peel strength The peel strength was measured in accordance with JIS C 6481.

As is apparent from the table, Examples 1 to 6 are compounds containing two or more maleimide groups in the molecule, one or more styryl groups and one or more phenolic hydroxyl groups in the molecule, A laminated board using the resin composition for circuit boards of the present invention of an epoxy resin containing one or more epoxy groups in the molecule, excellent in solder heat resistance and adhesion, and having a sufficient dielectric constant and dielectric loss tangent It was a low value.
In contrast, Comparative Example 1 used a cyanate resin in place of a compound containing one or more styryl groups and one or more phenolic hydroxyl groups in the molecule, but the solder heat resistance deteriorated after moisture absorption. 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 and one or more phenolic hydroxyl groups in the molecule, the dielectric constant and dielectric loss tangent were sufficiently low. did not become. Moreover, since the comparative example 3 did not use the epoxy resin which contains one or more epoxy groups in a molecule | numerator, adhesiveness deteriorated.

  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 (7)

A compound (A) containing two or more maleimide groups in the molecule;
Following general formula (1) one styryl group and one phenolic hydroxyl group containing compound in the molecule represented by (B), and
Epoxy resin containing one or more epoxy groups in the molecule (C)
A resin composition for circuit boards, comprising:
The resin composition for a circuit board according to claim 1, wherein the compound (A) is 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane. The resin composition for circuit boards according to claim 1, wherein the compound (A) is bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane. Said circuit cured product of the substrate for the resin composition, the dielectric constant at 1GHz is 2.3 or more, the circuit board resin composition according to any one of claims 1 to 3 is 3.5 or less. Said circuit cured product of the substrate for the resin composition, the dielectric loss tangent at 1GHz is 0.005 or more, the circuit board resin composition according to any one of claims 1 to 4 is 0.018 or less. Claims 1 to 5 or prepreg circuit board, wherein the circuit board resin composition to become impregnated into the base material according to one of. A laminate comprising one or more prepregs for a circuit board according to claim 6 .