JP4622280B2 - Resin composition, prepreg and laminate - Google Patents

Description

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

  Information processing devices such as notebook personal computers and mobile phones are required to be faster and have a higher CPU clock frequency. For this reason, a circuit board used in such information processing equipment is also required to have a high signal propagation speed, and is required to be a laminate having a low dielectric constant and low dielectric loss tangent, which is advantageous for the high speed.

  Cyanate resin is used as a resin having excellent heat resistance and excellent dielectric properties. Since the cyanate resin does not generate a reactive group having a large polarization such as a hydroxyl group by a curing reaction, the dielectric property is very excellent (for example, Patent Document 1).

  As a curing catalyst for the cyanate resin, amine compounds, phenol compounds, various metal complexes, and the like are used. However, these curing catalysts have a drawback that their catalytic activity is deactivated in a short time and curing is insufficient depending on conditions.

Japanese Patent No. 3310426

  An object of the present invention is to provide a resin composition, a prepreg, and a laminate obtained from the prepreg, which are excellent in heat resistance and dielectric properties and excellent in storage stability.

Such an object is achieved by the present invention described in the following (1) to ( 3 ).
(1) by impregnating the base material with a resin composition used to form a prepreg sheet, a resin wherein the bisphenol A type cyanate resin, to include f hexa ammine cobalt (III) acetate composition object.
(2) A prepreg comprising a base material impregnated with the resin composition described in (1 ) above.
(3) A laminate comprising one or more of the prepregs described in ( 2 ) above.

  The present invention is a resin composition containing a cyanate resin and a hexacoordinate trivalent cobalt complex, and a prepreg and a laminate using the resin composition. Compared to conventional ones, sufficient heat resistance, dielectric properties, Preservability can be expressed.

The resin composition of the present invention is a resin composition used for forming a sheet-like prepreg by impregnating a base material, comprising a cyanate resin and a hexacoordinate trivalent cobalt complex It is.
Moreover, the prepreg of the present invention is characterized in that a base material is impregnated with the above-mentioned resin composition.
Moreover, the laminated board of the present invention is formed by molding one or more of the above-described prepregs.
First, the resin composition of the present invention will be described.

  The resin composition of the present invention contains a cyanate resin. Thereby, the heat resistance and dielectric properties of the resin composition and the like can be improved.

Although it does not specifically limit as cyanate resin used by the resin composition of this invention, For example, a novolak-type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, tetramethylbisphenol F type cyanate resin etc. can be mentioned. .
Among these, bisphenol A type cyanate resin is preferable from the viewpoint of versatility and adhesion, and novolak type cyanate resin is preferable from the viewpoint of heat resistance.

  Although content of the said cyanate resin is not specifically limited, 60 weight% or more of the whole resin composition is preferable. If the content is less than the lower limit, heat resistance and dielectric properties may not be sufficient.

  The resin composition of the present invention contains a hexacoordinate trivalent cobalt complex compound. Thereby, the preservability of the resin composition can be improved.

Examples of conventionally known cyanate resin catalysts include amine compounds and phenol compounds. However, these compounds also cause side reactions other than the cyclization reaction of cyanate, and thus may not exhibit sufficient dielectric properties.
Moreover, although metal complex compounds, such as manganese and zinc, are also used as a catalyst, there was a defect that the ligand exchange reaction was easily caused in the varnish, and the varnish storage stability was poor.

In contrast, the present inventors have found that these problems can be solved by using a hexacoordinate trivalent cobalt complex as a catalyst for the cyanate resin.
The reason is that the hexacoordinate trivalent cobalt complex has high stability, is not oxidized with water or air, and has a low ligand exchange reaction at room temperature, so that the preservability of the resin composition is excellent. And since a ligand exchange reaction fully occurs at high temperature, it has sufficient catalytic activity.

Various examples of the hexacoordinate trivalent cobalt complex include trisacetylacetonate cobalt (III), hexaamminecobalt (III) acetate, trisethylenediaminecobalt (III) acetate, pentaamminenitrosylcobalt ( III) acetate and the like.
Among these, a ligand containing a bidentate or higher ligand is preferable, and a hexacoordinate trivalent cobalt complex in which all ligands are bidentate or higher ligands is particularly preferable. In particular, trisacetylacetonate cobalt (III) is preferable from the viewpoint of solubility in a solvent.

Although content of the said hexacoordinate trivalent cobalt complex is not specifically limited, It is preferable that it is 0.05-0.20 weight part with respect to 100 weight part of whole resin.
If the content of the hexacoordinate trivalent cobalt complex is less than the lower limit, curing may be insufficient and heat resistance may deteriorate, and if it exceeds the upper limit, moldability may be reduced.

  The resin composition of the present invention contains the above-described cyanate resin and a hexacoordinate trivalent cobalt complex as essential components. However, other resins, coupling agents, other Ingredients can be added. For example, when an epoxy resin is used in combination, adhesion and low water absorption are improved.

Next, the prepreg will be described.
The prepreg of the present invention is obtained by impregnating a base material with the above resin composition. 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.

  Examples of the method of impregnating the substrate with the resin composition obtained in the present invention include, for example, a method in which a resin varnish is prepared by dissolving the resin composition in a solvent, and the substrate is immersed in the resin varnish. The method of apply | coating a varnish to a base material, the method of spraying a resin varnish on a base material with a spray apparatus, etc. are mentioned. Among these, the method of immersing the base material in the resin varnish is preferable. Thereby, the impregnation property of the resin composition 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 for the resin varnish desirably has good solubility in the resin composition, but a poor solvent may be used as long as it does not adversely affect the resin varnish. Examples of the solvent exhibiting good solubility include methyl ethyl ketone and dimethylformamide.
Although the solid content in the resin varnish is not particularly limited, the solid content of the resin composition is preferably 40 to 80% by weight, and particularly preferably 50 to 65% by weight. Thereby, the impregnation property to the base material of the resin varnish can further be improved.
A prepreg can be obtained by impregnating the base material with the resin composition 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. This
A laminate having excellent dielectric properties and heat resistance 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 prepregs.
Next, a laminate can be obtained by heating and pressurizing a laminate of a prepreg and a metal foil.
Although the temperature to heat is not specifically limited, 120-220 degreeC is preferable and especially 150-200 degreeC is preferable.
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.

( Comparative Example 5 )
(1) Preparation of resin varnish Dimethylformamide was added to 100 parts by weight of bisphenol A type cyanate resin (B-40S manufactured by Ciba Geigy Co.) and 0.16 part by weight of trisacetylacetonate cobalt (III), and the nonvolatile content concentration was 55% by weight. A resin varnish was prepared as follows.

(2) Production of prepreg Using the above 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 the resin varnish as a solid content. It was dried in a drying furnace at 150 ° C. for 5 minutes to obtain a prepreg having a resin content of 44.4 wt%.

(3) Manufacture of laminated plate Six prepregs are stacked, and an electrolytic copper foil having a thickness of 35 μm is stacked on the top and bottom, and pressure and pressure molding is performed at a pressure of 4 MPa, a temperature of 200 ° C. for 120 minutes, and a temperature of 220 ° C. for 60 minutes. A double-sided copper clad laminate having a thickness of 1.2 mm was obtained.

(Example 2 )
( Reference Example 1 )
80.0 parts by weight of bisphenol A-type cyanate resin, 20 parts by weight of brominated bisphenol A-type epoxy resin (153 manufactured by Dainippon Ink & Chemicals, Inc.), trisacetylacetonate cobalt (III) A resin varnish was prepared in the same manner as in Example 1 except that the amount was 0.06 part by weight, and a prepreg and a laminate were obtained.

( Reference Example 2 )
The same procedure as in Example 1 was conducted except that the amount of phenol novolac cyanate resin (PT-60 manufactured by Lonza) was 100 parts by weight and the amount of trisacetylacetonate cobalt (III) was 0.08 parts by weight. A resin varnish was prepared to obtain a prepreg and a laminate.

Example 4
A resin varnish was prepared in the same manner as in Example 1 except that the amount of bisphenol A-type cyanate resin was 100 parts by weight and the amount of hexaamminecobalt (III) acetate was 0.08 parts by weight. I got a plate.

(Comparative Example 1)
A resin varnish was prepared in the same manner as in Example 1 except that cobalt naphthenate was used instead of trisacetylacetonatocobalt (III) and the blending amounts shown in Table 1 were used, and a prepreg and a laminate were obtained.

(Comparative Example 2)
A resin varnish was prepared in the same manner as in Example 1 except that zinc naphthenate was used instead of trisacetylacetonatocobalt (III) and the blending amounts shown in Table 1 were used, and a prepreg and a laminate were obtained.

(Comparative Example 3)
A resin varnish was prepared in the same manner as in Example 1 except that 2-methylimidazole was used in place of trisacetylacetonate cobalt (III) and the blending amounts shown in Table 1 were used, and a prepreg and a laminate were obtained.

(Comparative Example 4)
A resin varnish was prepared in the same manner as in Example 3 except that cobalt naphthenate was used instead of trisacetylacetonatocobalt (III) and the blending amounts shown in Table 1 were used, and a prepreg and a laminate were obtained.

  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) Glass transition temperature The glass transition temperature was determined from the peak temperature of tan δ by a viscoelastic method.

(2) Dielectric properties The dielectric constant and dielectric loss tangent were measured in accordance with JIS C 6481 and measured by measuring the capacitance at a frequency of 1 MHz.

(3) Solder heat resistance The solder heat resistance was measured in accordance with JIS C 6481. The measurement was performed after boiling for 2 hours and then immersed in a solder bath at 260 ° C. for 120 seconds, and then examined for abnormal appearance.

(4) Gel time change rate of resin varnish The gel time change rate of resin varnish is the gel time at 170 ° C. immediately after adjustment of the resin varnish (t ₁ ) and the gel time at 170 ° C. after leaving the resin varnish at 25 ° C. for 24 hours. From (t ₂ ), the following formula was used.
Gel time change rate (%) = 100 × [(t ₁ −t ₂ ) / t ₁ ]

Notes to table (1) Bisphenol A type cyanate resin (Brand name: B-40S manufactured by Ciba Geigy)
(2) Phenol novolac type cyanate resin (trade name: PT-60 manufactured by Lonza)
(3) Brominated epoxy resin (trade name: 153 manufactured by Dainippon Ink & Chemicals, Inc.)
(4) Trisacetylacetonate cobalt (III)
(5) Hexaamminecobalt (III) acetate

As is apparent from the table, Example 4 was excellent in heat resistance, dielectric properties, and storage stability. On the other hand, since Comparative Examples 1-4 did not use a hexacoordinate trivalent cobalt complex, it resulted in inferior varnish preservability.

  The resin composition, prepreg, and laminate of the present invention are suitable for printed wiring boards that can cope with a reduction in size and weight and require high heat resistance and dielectric properties.

Claims (3)

By impregnating a base material a resin composition used to form a prepreg-like sheet, the resin composition comprising a bisphenol A type cyanate resin, to include f hexa ammine cobalt (III) acetate. A prepreg comprising a substrate impregnated with the resin composition according to claim 1 . A laminate obtained by molding one or more prepregs according to claim 2 .