JP2010254790A - Resin composition for circuit board, prepreg, and laminated board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for a circuit board, which has a low dielectric constant and a dielectric tangent, as well as excellent heat resistance and adhesiveness; and a prepreg and a laminate using the same. <P>SOLUTION: The resin composition for the circuit board comprises a compound containing two or more maleimide groups in the molecule, a 2,2,4-trimethyl-1,2-dihydroquinoline polymer, and an aromatic compound having two or more hydroxyl groups in the ortho position, wherein the aromatic compound having two or more hydroxyl groups in the ortho position is 2,3-dihydroxynaphthalene. <P>COPYRIGHT: (C)2011,JPO&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.

  As a resin composition having both heat resistance and dielectric properties, a compound having two or more maleimide groups in a molecule and an aromatic diamine compound are generally reacted. In order to obtain excellent dielectric properties, it is necessary to reduce the nitrogen content of aromatic diamines as much as possible, and to increase the amino group equivalent as much as possible. However, since the amino group equivalent of aromatic diamines is generally less than 100, the nitrogen content cannot be sufficiently reduced, and excellent dielectric properties cannot be obtained. In addition, when aromatic diamines having a large amino group equivalent are used in order to reduce the nitrogen content of aromatic diamines, the crosslinking density is lowered and sufficient heat resistance cannot be obtained.

JP-A-5-86138 Japanese Patent Laid-Open No. 5-170950 JP-A-5-170951 Japanese Patent Application Laid-Open No. 11-21351

  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 (4).
(1) A compound containing two or more maleimide groups in the molecule, a 2,2,4-trimethyl-1,2-dihydroquinoline polymer, and an aromatic compound having two or more hydroxyl groups in the ortho position A resin composition for circuit boards, comprising:
(2) The resin composition for a circuit board according to (1), wherein the aromatic compound having two or more hydroxyl groups at the ortho position is 2,3-dihydroxynaphthalene.
(3) The circuit board resin composition according to (1), wherein the aromatic compound having two or more hydroxyl groups at the ortho position is 1,2-dihydroxynaphthalene.
(4) The resin composition for a circuit board according to (1), wherein the aromatic compound having two or more hydroxyl groups at the ortho position is pyrogallol.
(5) The resin composition for a circuit board according to (1), wherein the aromatic compound having two or more hydroxyl groups at the ortho position is catechol.
(6) The resin composition 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 loss tangent at 1 GHz of 0.005 or more and 0.015 or less. object.
(7) A prepreg obtained by impregnating a base material with the resin composition for circuit boards according to any one of (1) to (6).
(8) A laminate obtained by molding one or more prepregs according to (7).

  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 2,2,4-trimethyl-1,2-dihydroquinoline polymer, and two or more ortho-positions. It contains an aromatic compound having a hydroxyl group.

  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 the present invention contains a compound containing two or more maleimide groups in the molecule.

  The compound containing two or more maleimide groups in the molecule 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 And bismaleimides such as N, N′-hexamethylene dimaleimide and polymaleimides 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 compounds containing two or more maleimide groups in the molecule may be used alone or in combination of two or more.

  The resin composition for circuit boards of the present invention contains a 2,2,4-trimethyl-1,2-dihydroquinoline polymer. Thereby, the glass transition point can be improved while maintaining a low dielectric loss tangent, and high adhesion can be exhibited.

  The 2,2,4-trimethyl-1,2-dihydroquinoline polymer has a large amino group equivalent of about 170 with respect to a compound containing two or more maleimide groups in the molecule, and a low nitrogen content. Will not be adversely affected. In addition, since the dihydroquinoline structure is rigid, molecular motion is suppressed and a low dielectric loss tangent is expressed.

  Since the 2,2,4-trimethyl-1,2-dihydroquinoline polymer has two or more secondary amino groups in the molecule, it reacts with a compound containing two or more maleimide groups in the molecule. In addition, a network structure is formed. Moreover, since the dihydroquinoline structure is a rigid structure, the glass transition point can be improved and sufficient heat resistance is expressed.

  Since 2,2,4-trimethyl-1,2-dihydroquinoline polymer has a nitrogen atom in the molecule, it has high adhesion when reacted with a compound containing two or more maleimide groups in the molecule. .

  The equivalent ratio of the compound containing two or more maleimide groups in the molecule and the 2,2,4-trimethyl-1,2-dihydroquinoline polymer 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.

  As the 2,2,4-trimethyl-1,2-dihydroquinoline polymer, those having various polymerization degrees and purity can be used. As the 2,2,4-trimethyl-1,2-dihydroquinoline polymer, a commercially available product can be used, or it can be synthesized by the method of JP-A-10-13938.

  The resin composition for a circuit board of the present invention contains an aromatic compound having two or more hydroxyl groups at the ortho position. Thereby, the reaction of the compound containing two or more maleimide groups in the molecule and the 2,2,4-trimethyl-1,2-dihydroquinoline polymer can be promoted.

  In an aromatic compound having two or more hydroxyl groups in the ortho position, hydrogen ions are easily released, and hydrogen ions are added to the C—C double bond of a compound having two or more maleimide groups in the molecule. The nitrogen atom of the 2,2,4-trimethyl-1,2-dihydroquinoline polymer can easily attack the C—C double bond, and the reaction can be promoted.

  In addition, an aromatic compound having two or more hydroxyl groups at the ortho position can suppress high self-polymerization of a compound having two or more maleimide groups in the molecule, so that high adhesion can be maintained.

  The aromatic compound having two or more hydroxyl groups at the ortho position is not particularly limited, but catechol, 3-chlorocatechol, 3-methoxycatechol, 3-methylcatechol, 4-methylcatechol, 4-t-butylcatechol, Examples include 3,5-di-t-butylcatechol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene.

  From the viewpoint of melting point and volatility, 1,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene are preferred, and pyrogallol is preferred from the viewpoint of reaction promotion.

  The dielectric loss tangent at 1 GHz of the cured product of the circuit board resin composition of the present invention is preferably 0.005 or more and 0.015 or less.

  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 a cured product of such a resin material, for example, it is preferably treated at 120 to 220 ° C. for 30 to 180 minutes, and particularly preferably treated at 180 to 230 ° C. for 45 to 120 minutes.

  The resin composition for a circuit board according to the present invention includes a compound containing two or more maleimide groups in the molecule, a 2,2,4-trimethyl-1,2-dihydroquinoline polymer, and two or more in the ortho position. An aromatic compound having a hydroxyl group is contained as an essential component, but other resins, curing agents, curing accelerators, flame retardants, coupling agents, fillers, and other components are added as long as they do not contradict the purpose of the present invention. You can do it.

  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 N-methylpyrrolidone and the like.

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 63.0 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane, 2,2,4-trimethyl-1,2-dihydroquinoline polymer (Ouchi Emerging Chemical's Nocrack 224) was adjusted to 35.9 parts by weight and 2,3-dihydroxynaphthalene to 1.1 parts by weight with N-methylpyrrolidone to a nonvolatile content of 55% 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 prepared by drying in a drying oven for 7 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)
65.4 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane, 33.6 parts by weight of 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 2,3 A resin varnish was prepared in the same manner as in Example 1 except that 1.0 part by weight of dihydroxynaphthalene was used, and a prepreg and a laminate were obtained.
(Example 3)
2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane 58.1 parts by weight, 2,2,4-trimethyl-1,2-dihydroquinoline polymer 40.7 parts by weight, 2,3 A resin varnish was prepared in the same manner as in Example 1 except that 1.0 part by weight of dihydroxynaphthalene was used, and a prepreg and a laminate were obtained.
Example 4
56.1 parts by weight of bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane, 42.9 parts by weight of 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 2,3 A resin varnish was prepared in the same manner as in Example 1 except that 1.0 part by weight of dihydroxynaphthalene was used, and a prepreg and a laminate were obtained.
(Example 5)
63.0 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane, 35.9 parts by weight of 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 1,2 -A resin varnish was prepared in the same manner as in Example 1 except that dihydroxynaphthalene was changed to 1.1 parts by weight to obtain a prepreg and a laminate.
(Example 6)
63.4 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane, 36.1 parts by weight of 2,2,4-trimethyl-1,2-dihydroquinoline polymer, and 0 of pyrogallol A resin varnish was prepared in the same manner as in Example 1 except that the amount was 6 parts by weight, and a prepreg and a laminate were obtained.
(Comparative Example 1)
Resin in the same manner as in Example 1 except that 84.1 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane and 15.9 parts by weight of 4,4′-diaminodiphenylmethane were used. A varnish was prepared to obtain a prepreg and a laminate.
(Comparative Example 2)
Except for 75.3 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane and 24.7 parts by weight of 4,4 ′-(p-phenylenediisopropylidene) dianiline. A resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg and a laminate.
(Comparative Example 3)
Except for using 72.0 parts by weight of bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane and 28.0 parts by weight of 4,4 ′-(p-phenylenediisopropylidene) dianiline. 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.

（表の注）
１）大内新興化学製ノクラック２２４
１．評価方法
（１）樹脂の１ＧＨｚでの誘電特性測定
樹脂の１ＧＨｚでの誘電特性測定は、回路基板用樹脂組成物をキャリアフィルムに塗工し、加熱し、プレスした後にキャリアフィルムを除去したものを、トリプレート共振器法で測定した。
（２）積層板の１ＧＨｚでの誘電特性測定
積層板の１ＧＨｚでの誘電特性測定は、トリプレート共振器法で測定した。
（３）ガラス転移温度
ガラス転移温度は、ＴＭＡにて熱膨張係数を測定し、熱膨張係数の変移点をガラス転移温度とした。
（４）ピール強度
ピール強度は、ＪＩＳ Ｃ ６４８１に準拠して測定した。

(Note to table)
1) Nouchi 224 manufactured by Ouchi Shinsei Chemical
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) Glass transition temperature As for the glass transition temperature, the thermal expansion coefficient was measured by TMA, and the transition point of the thermal expansion coefficient was taken as the glass transition temperature.
(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 having two or more maleimide groups in the molecule, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, and two in the ortho position. It is a laminated board using the resin composition for circuit boards of the present invention containing the aromatic compound having the above hydroxyl group, and has a sufficiently low dielectric constant and dielectric loss tangent, a high glass transition temperature, and excellent adhesion. It was.
In contrast, Comparative Examples 1, 2, and 3 contain an aromatic diamine compound instead of the 2,2,4-trimethyl-1,2-dihydroquinoline polymer, and two or more maleimide groups in the molecule. However, the dielectric constant and dielectric loss tangent were not sufficiently low, and the adhesion was not sufficient.

  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 (8)

  Having a compound containing two or more maleimide groups in the molecule, a 2,2,4-trimethyl-1,2-dihydroquinoline polymer, and an aromatic compound having two or more hydroxyl groups in the ortho position. A resin composition for a circuit board.   The resin composition for a circuit board according to claim 1, wherein the aromatic compound having two or more hydroxyl groups at the ortho position is 2,3-dihydroxynaphthalene.   The resin composition for a circuit board according to claim 1, wherein the aromatic compound having two or more hydroxyl groups at the ortho position is 1,2-dihydroxynaphthalene.   The resin composition for a circuit board according to claim 1, wherein the aromatic compound having two or more hydroxyl groups at the ortho position is pyrogallol.   The resin composition for a circuit board according to claim 1, wherein the aromatic compound having two or more hydroxyl groups at the ortho position is catechol.   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 loss tangent at 1 GHz of 0.005 or more and 0.015 or less.   A prepreg obtained by impregnating a base material with the circuit board resin composition according to claim 1.   A laminate obtained by molding one or more prepregs according to claim 7.